TVGuide.com said Fey made the casting announcement Thursday on NPR's "Leonard Lopate Show."
"We have another few amazing cameos," Fey said. "One, I'm going to make an executive decision that I'm allowed to talk about this -- we have Condoleezza Rice coming up in a couple weeks on the show."
Fey revealed Rice is to play the former flame of Alec Baldwin's character Jack, TVGuide.com said.
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