Arnett, 55, and Poehler, 54, are both nominated in the inaugural Best Podcast category at this year's awards show for their programs SmartLess and Good Hang, respectively.
Speaking exclusively for an interview with PEOPLE 10 alongside his Is This Thing On costar Laura Dern, Arnett implied that Poehler might be the one to go home victorious.
When asked if he had already planned an acceptance speech, Arnett joked that he would "leave the speech writing" to his co-host Sean Hayes, and when Dern, 58, teased that Hayes, 55, has "actually written all the speeches for all the nominees for every category," Arnett responded with a hint that he thinks his ex could be the winner.
"Yeah. He's written Amy's acceptance speech already," the Arrested Development star said. (He and Hayes are joined on their podcast by Jason Bateman.)
Arnett first met Poehler in the 1990s when he saw the SNL alum’s improv group perform in New York City. The pair didn’t connect romantically until 2000 when they were re-introduced by mutual friends.
They later wed in 2003, and the former couple went on to welcome two sons together, Archie in 2008 and Abel in 2010.
Poehler and Arnett decided to go their separate ways after nine years of marriage in 2012. Their divorce was officially finalized in 2016.
Poehler reflected on the split in her 2014 memoir, Yes Please, stating that she didn't plan to share much about it in the book because she found it "too sad and too personal."
However, the Parks and Recreation star wrote that there were "a few things" she wanted to clear up.
"I am proud of how my ex-husband, Will, and I have been taking care of our children; I am beyond grateful he is their father; and I don't think a [nearly] ten-year marriage constitutes failure," she wrote. "That being said, getting a divorce really sucks."
Poehler appeared on the 250th episode of SmartLess back in April, when Arnett took the opportunity to share how grateful he is to still have his ex-wife in his life as a friend.
"I'm really, really lucky to have her as a partner in this way. There aren't many people I speak to more than I speak to her, which is weird -- you know what I mean? But it's great," Arnett said. "She is somebody that I still run a lot of stuff by."
He continued, "She's the person I go to, like, 'Hey, I'm thinking about doing this.' Whether it's life or work, I really seek her counsel because it's important to me -- because I trust her. She's awesome."
While Arnett has been in the podcasting game since 2020, Poehler is relatively new to the medium, as Good Hang premiered in March.
The other nominees in the Best Podcast category at this year's Golden Globes include: Armchair Expert with Dax Shepard, Call Her Daddy, The Mel Robbins Podcast and NPR's Up First.
The 83rd annual Golden Globe Awards will take place at the Beverly Hilton in Los Angeles on Sunday, Jan. 11 at 8 p.m. EST, airing on CBS and streaming on Paramount+.