Rebel troops found the photo album while raiding Gaddafi's compound in Tripoli, Sky News reported.
Gaddafi had earlier expressed strong feelings for Rice in a TV interview in 2007 with Al Jazeera.
"I admire and am very proud of the way she leans back and gives orders to the Arab leaders," Gaddafi was quoted as saying.
"Leezza, Leezza, Leezza... I love her very much. I admire her and am proud of her because she's a black woman of African origin," he said.
Gaddafi met Rice in 2008 when she visited Libya in an attempt to cool relations between the two countries.
She even spent time at his home, and shared a traditional meal during the Muslim holy month of Ramadan.
Rice was later given a number of "unusual and expensive" gifts - including a diamond ring and a locket with Gaddafi's likeness engraved inside, Sky News said.
Rice - currently an academic at Stanford University - has not responded to questions.
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