Meeting a day after the end of a summit of African and South American leaders in Venezuela, the two men signed a declaration urging a global conference be held to sketch out new terms defining terrorism.
Neither spoke publicly about the document, which rejects "attempts to link the legitimate struggle of the people for liberty and self-determination" with terrorism, according to a Venezuelan government website.
Chavez, has faced U.S. and Colombian charges he backs FARC Marxist rebels in Colombia. He denies the allegations.
Gaddafi, who has ruled Libya for 40 years professing "Islamic socialism," has been accused of harboring terrorists. But he has sought to improve relations with the United States after he said he was abandoning his country’s nuclear, chemical and biological weapons programs in 2003.
Chavez repeatedly feted Gaddafi during the Libyan leader’s first visit to Latin America.
The two rallied hundreds of Venezuelans on Monday on Venezuela’s Margarita Island, where Chavez presented Gaddafi with a replica of a sword of South American independence hero Simon Bolivar.
"We’re writing new pages of history. We are here to change history and create a new socialism, a new world," Chavez said.
On Monday, Gaddafi could be seen shopping on Margarita wearing an African-motif shirt, occasionally stopping to mingle with ordinary Venezuelans.