And if the new promo for his upcoming episode is any indication, the Spider-Man: No Way Home star is planning to bring some of that villainous charm to the iconic studio 8H stage with him.
Dafoe was joined by SNL's Chris Reed -- as well as this week's musical guest, Katy Perry -- where he couldn't help but share his excitement at hosting for the first time.
"Oh man, I love this sketch already," Dafoe says with a chuckle. "Oh no, Willem, this is just a promo," Reed responds. "Hey, whatever you call it, it's hilarious," Dafoe quips, letting out a menacing laugh.
That excitement continued later on in the promo when the 66-year-old actor shared his "premonition" for this weekend's show.
"Man, I'm having a major déjà vu. Have we done this before?" he asks Reed and Perry. "No, no no," the "When I'm Gone" singer replies. "Nah, I don't think so," Reed agrees.
"It must have been a premonition I had...," Dafoe adds before throwing on a pair of sunglasses. "About the best night of my entire life!"
"That's right!" Perry yells out.
While this will be Dafoe's first time hosting the sketch comedy show, it's not his first time on the SNL stage.
"I'm so sorry, Will. There's been a mistake," show creator Lorne Michaels said, as Dafoe stepped out of the shadows behind him.
When Forte explained that he thought Dafoe was supposed to be hosting next week, Lorne said incredulously, "You think I'd book someone named Will, then someone named Willem?"
Ultimately, Lorne jokingly explained that he'd texted Forte to come host the show by accident, as he texted "Willem" and the phone's autocorrect made the change.
Perry's no stranger to the stage either, with Saturday marking her fifth appearance on the long-running program -- the GRAMMY-winning artist has been a musical guest on the show three times before, and hosted back in 2011.