Barrymore, who was reportedly with Love that night, said she doesn't remember the specifics of the incident but speculated about Love's motivations.
"Let me just fill in the banks, having known Courtney back then," the star said. "You know, Courtney was like an animal. She loved to spar. I'm sure she had some type of beef with Madonna, or vice versa, and Courtney couldn't sweep anything under a rug to save her life. It was sort of all out there."
"That's what we loved about her, was we were sick of everyone pretending to be so plastic and perfect, and out comes this creature who's just, like, raw," she added. "So that's probably why. I'm sure she just had an issue and thought, 'I'm going to throw my compact at her.'"
Madonna was giving an interview on the MTV VMAs red carpet when Love threw her compact at the pop star.
"Courtney Love is in dire need of attention right now," Madonna told the interviewer. "She's throwing her compact at me."
The interview host invited Love to join him and Madonna on the dais, where Love accused Madonna of being "mean" to her.
On WWHL, Barrymore also discussed the challenges of online dating. She said she got stood up and didn't match with anyone on the dating app Raya.
"My friends sort of gave me this false sense of confidence," Barrymore said. "It was a car wreck. But I love being able to be in the conversation, I have to say. I definitely had fun with it."