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On the Queen’s Birthday Honours list, the name stood out from those of charity workers, teachers and civil servants: Angelina Jolie – Honorary Dame Commander of the Most Distinguished Order of St Michael and St George, for her campaigning work “for services to UK foreign policy and the campaign to end war zone sexual violence”. This means that the Hollywood A-lister has become one of a tiny group of US citizens to be honoured by the British establishment (though they can’t use their titles).

It was an extraordinary accolade – doubly so when you consider that the demure Jolie, who last week hosted a London summit dedicated to ending war rape in her capacity as special envoy for the United Nations High Commissioner for Refugees, is the same Jolie who, not long ago, was making headlines for her tattoos, hard-drug use and intimately kissing her brother in public.

Then she was a twice-divorced, self-confessed bisexual and self-harmer. But in just 14 years, Jolie, 39, has dramatically reinvented herself, from out-of-control starlet and apparent homewrecker (actor Brad Pitt left his wife Jennifer Aniston after meeting Jolie on the set of their film Mr & Mrs Smith) to devoted mother and humanitarian powerhouse, travelling to war zones such as Congo with William Hague, the Foreign Secretary.

Her youthful recklessness has transmuted into selfless bravery. Her unauthorised biographer, Andrew Morton, whose most famous subject was Diana, Princess of Wales, became intrigued after learning that she’d been working in Peshawar, Pakistan – “hardly a place for charity workers, let alone bona fide Hollywood movie stars,” he says. “We now see her as a humanitarian and a substantial, solid and serious-minded citizen of the world, not the woman who broke up Jen and Brad.”

Then, last year she underwent a preventative double mastectomy after testing positive for a gene linked to breast and ovarian cancers, which killed her mother at the age of 56. This gave Angelina a powerful voice in women’s health.

Indeed, so drastic has been her rehabilitation that Jolie’s status is now among the tiny section of Hollywood stars deemed untouchable. According to US pollster Q Scores, which determines celebrities’ likeability factor, Jolie’s score is 23 – meaning 23 per cent of US adults consider her “one of [their] favourite personalities”, while 85 per cent of adults know who she is. This compared with a 15 per cent likeability score and 46 per cent awareness for the average actress. Many of her films have performed poorly at the box office (though her latest,Maleficent, has earned $140 million in just three weeks), yet Jolie is considered one of the few female stars who can “carry” a film, and is estimated to be Hollywood’s highest-paid actress, earning $33 million last year.

“She’s hardly Meryl Streep, but the actual quality of her work is irrelevant. She’s Hollywood royalty, a megabrand,” says one film insider. Indeed, a recent poll named her, along with Pitt, as the celebrities most sought-after for endorsements. “Jolie has formed a strong emotional bond with American consumers, which is on the rise,” confirms Henry Schafer, executive vice-president of Q Scores.

Perhaps her appeal comes from her chameleon-like qualities. She has a sex-bomb persona (she is regularly named the world’s most beautiful woman by magazines such as Vogue) but is simultaneously a “madonna”, the mother of six children, three of whom are adopted.

“What’s remarkable about Jolie is she’s the best at everything she touches,” says Christina Hopkinson, author of The A-List Family. “When she was in her bad-girl phase, she was the baddest imaginable. Now she’s a mother, she’s the ultimate earth-mother of three boys and three girls – even her twins were the perfect boy-girl combination.

“She projects a cool, independent persona but she also appears to have a blissful home life with the ultimate movie star, Brad Pitt. She’s skinny but with big breasts – and you can’t even hate her for those breasts, because she’s had a mastectomy.”

Born in Los Angeles, Jolie is the daughter of actors Jon “Midnight Cowboy” Voight and the late Marcheline Bertrand, but her parents split when she was a baby as a result of Voight’s infidelities. Jolie and Voight’s relationship has been stormy ever since, with the pair not speaking for years at a time.

In contrast, she forged a possibly-too-close bond with her mother, who treated her like a friend, allowing Jolie to have a live-in lover from the age of 14.

Living in modest circumstances compared with her peers at Beverly Hills High School, Jolie was bullied. She became anorexic and began to self-harm, cutting herself with her collection of knives. Wearing only black clothes, she aspired to become a funeral director, taking a course in embalming. She decorated her body with 14 tattoos, including the Latin proverb quod me nutrit me destruit (“what nourishes me destroys me”). By the age of 20, she had tried “just about every drug possible”, including heroin.

At her first wedding, to British actor Jonny Lee Miller when she was just 20, she wore black rubber trousers and a white T-shirt, upon which she had written the groom’s name in her blood. Before they separated, Jolie had a relationship with an actress and has since confirmed her bisexuality to interviewers.

Four years later, she married actor Billy Bob Thornton after a two-month courtship. The pair wore each other’s blood in phials around their necks and for their first anniversary, she bought him his-and-hers cemetery plots in a Louisiana graveyard. Yet 18 months later they abruptly split.

By now Jolie was established, winning the best-supporting actress Oscar for her role in Girl, Interrupted. After the ceremony, she scandalised onlookers by passionately kissing her brother, actor James Haven, and telling the world, “I’m so in love with him”. Haven, for his part, is an unmarried, born-again Christian. He said: “Because I’m so close to Angie, it’s like I’ve already got the perfect woman in my life, and it’s hard for anyone else to live up to that.”

But just as tongue-wagging about her eccentricities was peaking, Jolie – then 26 – began visiting refugee camps. Her first trip to Sierra Leone was revelatory. “I realised how completely naive I was to think I had a difficult life,” she recalled. “It was as if someone slapped me across the face and said, 'Oh, my God, you silly young woman from California, do you have any idea how difficult the world really is for so many people?’ ”

The turning point, says Morton, came when she made Tomb Raider in 2001. “It was her rehab role, the actress weaning herself off heroin in order to sustain the physical demands of the movie,” he says. “During the filming, she decided to adopt a Cambodian boy named Maddox. The infant changed her life, she began focusing on him and her growing role as an international advocate for the United Nations High Commissioner for Refugees.”

In 2005, she adopted Zahara from Ethiopia (Pax, from Vietnam, arrived in 2007), that same year making Mr & Mrs Smith. Within months, Jolie and Pitt were visiting Pakistan together to solicit aid donations after an earthquake, and within a year Jolie was pregnant.

Yet her new reputation as a husband-stealer had no effect on Jolie’s popularity. Polls showed her kudos continued to rise year on year, despite Aniston describing Jolie’s behaviour as “uncool”, and the couple announced their engagement in 2012. Pitt has downplayed any suggestions that there was a “dastardly affair” and insists that his break-up with Aniston was amicable.

An executive on the Hollywood magazine Variety said: “She is perceived as somewhat saint-like – a woman who only wants to do good in the world. When you’re in her presence, she’s so serene, you’d feel like an idiot asking a dumb question, such as: 'So, did you break up Jennifer Aniston’s home?’ ”

Dorie Clark, author of Reinventing You: Define Your Brand, Imagine Your Future, uses Jolie as a prime example of reinvention. “Because her negative brand attributes centred around too much predatory sexuality,” she says, “motherhood and her clear devotion to her children showed a different, gentler side and balanced out her reputation.”

The couple’s fame rose as they travelled the world with their huge “rainbow family”, alternatively making films or doing good – be it campaigning to help New Orleans after Hurricane Katrina, or working in Haiti after the 2010 earthquake.

Many suspect that Jolie has brilliantly manipulated her narrative so the husband-stealing/wild-child persona has been airbrushed by the human saint. Whatever the motives, for more than a decade she’s travelled frequently to some of the most insalubrious corners of the world, bringing huge publicity to previously unfashionable causes.

“Frankly, if a celebrity isn’t genuinely interested in poverty and is simply trying to get good press, there are better ways to do it. Travelling to Darfur or Congo is dangerous, expensive and uncomfortable, and the outhouses have bats, scorpions and camel spiders,” says Nicholas Kristof of The New York Times, who spoke with Jolie at a 2008 session at the Council on Foreign Relations about justice in Darfur.

While she plays the celebrity game, it always seems to serve a higher purpose than personal vanity or greed. Pictures of her newborn twins were sold for a $14 million donation to her Jolie-Pitt Foundation. Those who have worked with her say her behaviour is strikingly un-divalike and professional.

Still, a suspicion persists that her youthful eccentricity (her father once tearfully described her as having “serious mental problems”) has never gone away, but that her restlessness is now being channelled to positive ends.

Now Jolie is reinventing herself again, as a director. Her latest, second, film Unbroken, about a Second World War hero, is hotly tipped as a 2015 Oscar contender. But before picking up another golden statue, there is the matter of a visit to Buckingham Palace to collect her gong.