Barrymore had previously sat with Green for the first time in 15 years on her show. Barrymore and Green were together from 1999 to 2001.
"There was no questions prepared for that. I had an offline conversation with him because we didn't want it to be some bougie Hollywood moment like, 'Let's reconnect in front of the cameras," Barrymore said on Tuesday.
Barrymore said she wanted to honor Green's career and how he filmed his life during a time when smartphones were not around, calling him a pioneer.
"I just wanted to have a lot of dignity and a gentle moment. And it was nice to hear from some people saying like, 'I'd like to have that with someone from my past,'" Barrymore said.
Barrymore also played Mad Lib Theater with Fallon. She chose a number of adjectives, verbs and other phrases that was later inserted into a comedic scene that involved Barrymore and Fallon meditating.