The Hollywood actress gained 2.1 million new followers in just three hours which beat Jennifer Aniston’s previous record for the quickest growth to 1million followers after making her Instagram debut in October 2019.
It took Ms Aniston five hours and 16 minutes to hit the one million mark.
In her first post, Ms Jolie shared a photograph of a heartbreaking letter from a teenage girl in Afghanistan who is now facing Taliban rule.
She also shared another photo of women wearing burkhas.
Alongside the letter, the 46-year-old wrote: “This is a letter I was sent from a teenage girl in Afghanistan. Right now, the people of Afghanistan are losing their ability to communicate on social media and to express themselves freely.
“So I’ve come on Instagram to share their stories and the voices of those across the globe who are fighting for their basic human rights.”
Many took to the comments to welcome the humanitarian to Instagram and to thank her for using her platform to spread awareness.
British Vogue editor-in-chief Edward Enninful said: “Thank you for using your platform for good.”
Actress Alyssa Milano wrote: “Thank you for being you.”
As of Saturday, the Tomb Raider actress has 4.9 million followers.
Meanwhile, Ms Aniston’s first post was a photo of her with Friends co-stars David Schwimmer, Matt LeBlanc, Lisa Kudrow, Matthew Perry and Courteney Cox.
She captioned: "And now we’re Instagram FRIENDS too, HI INSTAGRAM."
Ms Jolie and Ms Aniston were former love rivals, having both been married to Brad Pitt in the past.
Ms Aniston was married to the 57-year-old from 2000 to 2005.
Ms Jolie and Mr Pitt fell madly in love after his divorce from Ms Aniston.
They were a golden couple of Hollywood for nearly 12 years.
The couple wed in 2014 but they split two years later.
The duo have been locked in a custody battle since their divorce.