The former US secretary of state will appear in one episode before this month's season five finale, star and producer Tina Fey announced during an interview on NPR's Leonard Lopate Show on Thursday.
The former member of George W. Bush's cabinet will play herself as an ex-girlfriend of Alec Baldwin's character Jack Donaghy.
Donaghy has referenced his past romantic relationship with a "high-ranking African-American member of the Bush Administration" on the show before.
Rice previously revealed that she loves watching American Idol and said that the show relaxes her after foreign excursions.
Fey recently dismissed suggestions that Baldwin would not return to 30 Rock next season.