She was the National Security Advisor and then U.S. Secretary of State under George W. Bush, but did either of those jobs prepare Condoleezza Rice for Alec Baldwin?

We'll find out when the trend-setting Rice guest stars on NBC's 30 Rock.

She'll be playing herself in a story line that reveals she and Baldwin's character Jack Donaghy once had a fling THAT ended because he thought she'd become too flirty with Russian Prez Vladimir Putin.