It was some time during this banner year for both Green and Barrymore than the two first met (via Cheat Sheet). In 1999, Barrymore signed on to star in "Charlie's Angels" alongside Lucy Lu and Cameron Diaz, and she also worked on the film as a producer. Sometime during pre-production, Barrymore met Green and urged him to take a role in the movie. "She and the studio were trying to get me in that movie for a while," Green remembered while appearing on The Alan Cox Show in 2018. "I actually passed on it initially." He eventually let Barrymore persuade him, taking on the role of "The Chad," who helps the heroines of the film by transporting them on his strange little tugboat. And yes, he gets a kiss from Drew's character.

The couple began dating while filming the movie, which was released in 2000. They also became engaged and got married during that same year. Unfortunately, Green filed for divorce less than a year after the wedding, citing "irreconcilable differences" in 2001 (via In Style). At the time, there didn't seem to be bad blood, despite the divorce. At the time, Green said of his ex-wife, "Drew is a wonderful woman, I love her very much ... I wish our marriage could have worked out, I wish her much happiness."  Similarly, Barrymore released a statement saying, "I love Tom very much. He has always been a great friend and that won't change."