The footage was allegedly recorded soon after she had shot to fame with a Golden Globe WIN for Gia.
It has been released by a man named Franklin Meyer who has come forward claiming that he was the now 39-year-old actress' drug dealer while she lived in New York at the time.
Meyer has released the video to The National Enquirer, which he alleges depicts the star right after a drug buy as she talks frantically on the phone.
In the video, the Maleficent star paces back and forth in a dingy apartment as she talks frantically on the phone.
The television is on in the background as Angelina appears to be in a state of emotional distress as trash bags and soda cans litter the floor and coffee table.
Convicted drug dealer Meyer claims he shot the 16-minute footage with Jolie’s consent in 1999 after she called him round to her Manhattan home to re-supply her with heroin and cocaine.
‘Angie was a client of mine for several years. I sold her heroin and cocaine. One day she called me up and wanted me to drop by her place. That was her way of telling me she wanted me to bring her drugs,’ Meyer told the Enquirer.
‘At the time, I had just bought a video camera and decided to bring it along. When I arrived, I just gave her the drugs and then she gave me the money.’
Meyer, who has made previous claims about supplying the actress with drugs, said he kept filming her as her father, Hollywood star Jon Voight, rang and they discussed her brother, James, and late mother, Marcheline Bertrand. The footage, however, gives no clues as to who she is speaking with.
The Girl, Interrupted star can be heard saying: 'The thing is, you know, it’s that idea trying to get a house or a room for everybody. It’s not, it’s just not necessary.'
The conversation is hard to make out as it seems to involve an ongoing family issue: 'You know but it’s, you know it’s, whatever that house… I said once, well, what if I stop working? She’s like, telling me to relax, you know. But to, you know, I said what if I don’t work for you, what if I don’t make that much money? And you stay in an apartment until I make more money so that you can get a bigger house. What if something happens to me?'
'You know, I don’t want this to ruin our relationship,' she continued. 'And I don’t want it to be this thing where, you know, we go out to do something or to dinner or go shopping and you know, or her coming out to visit, and not buying something for herself.'
Adding: 'And I said to her, you know…we have to remind ourselves sometimes when we come to your place we talk about, you know, this concept…we’re all in this place, and it’s very hard for us to think about getting a house or these cars…when you have no new clothes, or that you have holes.'
She also appears to reference her brother James Haven as she talks about a 'Jamie' and calls herself his 'sister'.
The star looks painfully thin in the footage and a far cry from the humanitarian and respected activist she is today.
Meyer claims in the same interview that he would see Jolie two or three times a week when she was in the city, meeting either at her flat or at the hotel. Each time, she would generally spend around $100 on heroin and cocaine, he said.
According to Meyer, she would take the drugs in front of him. ‘It didn’t seem to matter to her who was there.’ On one occasion, he claimed, she was high on coke during a high profile TV interview to promote the 1999 film Girl, Interrupted for which she won an Oscar.
Meyer said Jolie, who at the time was seeing the actor Billy Bob Thornton, her future husband, was also startlingly open with him about her debauched sex life, including Thornton’s sexual prowess, her love of sado-masochism and her lesbian urges.
He says she confessed to having had a lesbian affair with actress Jenny Shimizu after they starred together in the 1996 film Foxfire. Jolie later told a magazine that she fell in love with Shimizu ‘the first second I saw her’.
The same year, the actress – who was still two years away from establishing herself as Hollywood’s premier pin-up star when she played adventuress Lara Croft – also posed for ‘lurid’ pictures taken by a friend.
According to the Enquirer, she ‘appears wasted – with black tape over her nipples and a dog leash around her neck’. In other suggestive shots, she is wearing a blindfold.
In 2011 Jolie alluded to a dark past as she told 60 Minutes: 'I went through heavier, darker times and I survived them. I didn't die young, so I’m very lucky. There are other artists and people who didn’t survive certain things.'
'I think people can imagine that I did the most dangerous and I did the worst,' she said at the time. 'For many reasons I shouldn’t be here. You think of those too many times where you came close to too many dangerous things, too many chances taken too far.'
MailOnline has reached out to Jolie's reps for comment.
Video is at the source.