During a game of "Brad or Ben" that required her to compare her two former flames, the Goop founder, 50, spoke up about her previous romances with the two stars during an appearance on the Call Her Daddy podcast broadcast Tuesday.
Paltrow dated Affleck from 1997 to 2000, while she was married to Pitt from 1994 to 1997.
During the game, host Alex Cooper, 29, questioned Paltrow who she thought was more romantic, who made her laugh the most, and who she was more likely to dispute with.
When asked which of the two was better in bed, Paltrow admitted the decision was "really hard."
"Brad was like the sort of major chemistry, love of your life, kind of, at the time, and then Ben was, like, technically excellent," she chuckled, adding, "I can't believe my daughter is listening to this!"
Cooper responded to Paltrow's candour by mentioning Affleck's wife Jennifer Lopez. "God bless J.Lo and everything she is getting over there!"
The Oscar winner also told the podcast host that Pitt, now 59, was the more romantic of the two, but Affleck, now 50, made her giggle — and with whom she was more likely to disagree.
She also said they were both "good kissers."
Paltrow's participation on Call Her Daddy isn't the first time she's spoken publicly about her relationship with the actor from Air.
During an appearance with Howard Stern's SiriusXM radio show in 2018, she opened out about the former couple's love story and the lessons she gained from it.
"It's interesting; I believe you're trying to work things out with certain boyfriends, right?" Paltrow responded. "Like, you're trying to heal certain things from your childhood, and he was a great teacher in that way."
"I'm not sure what I was trying to heal in that instance," she continued, "but it was...he was, you know, it was specific."
She told Stern a few years ago that Affleck "was not in a good place in his life to have a girlfriend" at the time they were together.
Paltrow was Affleck's first Hollywood collaborator after he won his first Oscar for Good Will Hunting in 1997 and burst into the scene. They met in 1997 at a dinner thrown by now-disgraced studio tycoon Harvey Weinstein, and went on to co-star in Shakespeare in Love in 1998 and Bounce in 2000.
In the years following, Paltrow has dated and married Coldplay's Chris Martin, with whom she has two children, Apple, 18, and Moses, 17. She and Martin divorced in 2014 in what they dubbed a "conscious uncoupling."
Paltrow later married Brad Falchuk, with whom she began a private relationship in 2014 and married in 2018.
In 2005, Affleck married Jennifer Garner, with whom he has three children: Violet, 17, Seraphina, 14, and Samuel, 11.
He and Garner split in 2015 and divorced three years later, but Affleck's love tale did not end there. He later reconnected with Lopez, with whom he had previously dated between 2002 and 2004.
The couple resumed their affair after reuniting in 2021, with Affleck proposing to Lopez in April 2022. They married twice that summer, once in Las Vegas and then again in Georgia.