Paltrow said she was left “petrified” after Weinstein propositioned her when she was just 22 while Jolie vowed never to work with him again after a “bad experience” as a young actress.
The high-profile pair join a growing list of stars accusing the producer of sexual harassment, while allegations of rape have also now emerged.
After he hired her as the lead in Emma, Paltrow claimed Weinstein summoned her to his suite at a Beverly Hills hotel where placed his hands on her and suggested they head to the bedroom for massages.
She told the New York Times: “I was a kid, I was signed up, I was petrified,” adding she confided in her then-boyfriend Brad Pitt who confronted Weinstein which led to him threatening her not to tell anyone else.
“I thought he was going to fire me,” Paltrow told the publication.
Pulp Fiction star Rosanna Arquette and French actress Judith Godreche made similar accusations according to the New York Times while Jolie said he made unwanted advances on her in a hotel room.
In an email statement to the publication, Jolie said: “I had a bad experience with Harvey Weinstein in my youth, and as a result, chose never to work with him again and warn others when they did.
“This behaviour towards women in any field, any country is unacceptable.”
On Tuesday three women alleged that Weinstein had raped them in an article in The New Yorker.
Actress Asia Argento and a former actress Lucia Evans went on the record to allege Weinstein forced himself on them sexually. A third woman spoke anonymously. Weinstein vehemently denied the allegations in a statement to the magazine.
The article also included an audio recording from 2015 made by the New York Police Department in which Weinstein admitted to groping model Ambra Battilana Guiterrez.
Former Democratic Presidential candidate Hillary Clinton, who received major donations from Weinstein during her presidential campaign, said she was “shocked and appalled” by the revelations.
In a post shared by her communications director Nick Merrill and retweeted by her, Secretary Clinton said: “The behaviour described by women coming forward cannot be tolerated.
“Their courage and the support of others is critical in helping to stop this kind of behaviour.”
Stars including George Clooney, Meryl Streep, Kate Winslet and Dame Judi Dench have thrown their support behind the women accusing him of sexual harassment while Ben Affleck said reading the rape allegations made him “sick”.
Affleck said he was “saddened and angry that a man who I worked with used his position of power to intimidate, sexually harass and manipulate many women over decades.”
He added: “The additional allegations of assault that I read this morning made me sick. This is completely unacceptable, and I find myself asking what I can do to make sure this doesn’t happen to others.
“We need to do better at protecting our sisters, friends, co-workers and daughters. We must support those who come forward, condemn this type of behaviour when we see it and help ensure there are more women in positions of power.”
Affleck launched his career through the success of 1997 film Good Will Hunting alongside Matt Damon which was produced and distributed through Weinstein’s former company, Miramax, and which won the pair a screenwriting Oscar.