Amy Poehler and Maya Rudolph are known for having great chemistry — but it took them time to get into their element.

The two “Saturday Night Live” alums told People in an interview published Wednesday that their favorite moment together from the legendary sketch show completely shifted the way they worked. Poehler said that thanks to a certain sketch, Rudolph helped her learn the “secret sauce” for success on the show.

When the two started at “SNL” in the early 2000s, they were both completely intimidated by the other, the actors told People.

“Amy came in and it was like [that scene in ‘Grease’] when the Pink Ladies get to school,” Rudolph said. “Amy was a beloved comic, and especially all the writer boys — and some of the writer girls — were like, ‘Amy tell us everything!’”

Poehler said the two had the “same impression about each other.”

“Because I was like, Maya is an ‘SNL’ natural,” she said. “Everything you need to do on this show, Maya can do it better than everyone.”

But their defenses quickly came down when they did a skit together in 2004 called “Trainwreck Awards,” in which Rudolph played Diana Ross and Poehler played the late Anna Nicole Smith. Rudolph told People that the sketch was “one of my favorite things Amy and I ever did.”

“You can tell we were truly laughing [in the sketch] because our wigs came off and people were nose breathing into their mics. … And I feel like that was the beginning of us recognizing, ‘Oh you can have a blast and do the show and laugh while you’re doing it?’” Rudolph said. “I think from then on we started to look for those opportunities and write in that way.”

Poehler said that the ability to find joy in goofing around onstage is “the gift that Maya gives me all the time, but definitely gave me at ‘SNL.’”

“And I think that, it’s kind of like the secret sauce to that show,” she said. “If you’re a performer and you look like you’re having fun, everyone relaxes and they have fun too.”

Since they left “SNL” they have gone on to work on multiple projects with one another. Rudolph and Poehler are currently sharing hosting duties on Peacock’s reality competition show “Baking It.”

They also worked together on Poehler’s 2019 directorial debut, “Wine Country,” in which Rudolph co-starred.

“She’s a natural born leader with kindness, humility, grace, love and she’s strong and disciplined. She’s tremendous,” Rudolph said of Poehler in an interview with E! News at the time. “We should take advantage of any chance we get to do this because as I grow in this life, the more time I spend away from my family, I just want to be with people that I want to spend my time with and these are people I deeply, deeply love.”