The late Libyan leader met Rice in the oil-rich north African country in September 2008, a historic meeting that signaled the once pariah state's return to the diplomatic table after decades of isolation.
Rice, unlike ex-British prime minister Tony Blair, declined to meet Gaddafi in his infamous tent, opting instead to hold talks in his residence.
"Obviously, the first visit by a US secretary of state since 1953 would be a major milestone on the country's path to international acceptability," wrote Rice in her book, "No Higher Honor," published online by The Daily Beast.
"But Gaddafi also had a slightly eerie fascination with me personally, asking visitors why his 'African princess,' wouldn't visit him."
Rice, who served under president George W. Bush, said she had been warned ahead of the meeting to ignore the Libyan leader's "crazy" behavior as he would eventually "get back on track." But her suspicions were soon confirmed.
"He suddenly stopped speaking and began rolling his head back and forth. 'Tell President Bush to stop talking about a two-state solution for Israel and Palestine!' he barked.
'It should be one state! Israeltine!'" Rice recalled.
"Perhaps he didn't like what I said next. In a sudden fit, he fired two translators in the room. 'Okay.' I thought, 'this is Gaddafi.'"
Rice's meeting with Gaddafi -- once described by former US president Ronald Reagan as a "mad dog" -- took place in Bab al Azizia, a Tripoli residence which was hit in US bombing raids ordered by Reagan in 1986.
It was there that the Libyan leader insisted Rice join him for dinner in his private kitchen, where he later presented her with a collection of photos of the US diplomat's meetings with world leaders -- set to the music of a song called "Black Flower in the White House," written for Rice by a Libyan composer.
"It was weird, but at least it wasn't raunchy," Rice said of the episode.
The talks were dominated by Gaddafi's decision to give up his weapons of mass destruction in 2003, in the wake of the September 11, 2001 attacks, and the need to secure a financial settlement for families of victims killed in the bombing by Libyan agents of Pan Am Flight 103 over Lockerbie, Scotland, in 1988.
"There was a clear diplomatic quid pro quo: in exchange, we'd help them to return to good standing in the international community. But it would not be easy and not only because of Gaddafi's long record of brutality," Rice said.
Libya did return to the international fold but the "Arab Spring" of 2011 would have consequences that, according to Rice, Gaddafi had not fully anticipated.
"I came away from the visit realizing how much Gaddafi lives inside his own head," Rice wrote.
"I wondered if he even fully understood fully what was going on around him. And I was very, very glad that we had disarmed him of his most dangerous weapons of mass destruction. There in his bunker, making his last stand, I have no doubt he would have used them," the former secretary of state said.