Sources in Caracas say that Nicolas Maduro, Venezuelan’s foreign minister, had discussed the offer with Amr Moussa, the head of the Arab League, and that details of the plan could be announced by the Arab League in Cairo on Thursday.
Mustafa Abdel Jalil, the head of the opposition National Libyan Council, told Al Jazeera he totally rejected the concept of talks with Gaddafi, and said that no one had been in contact with him regarding the Venezuelan initiative.
The plan would involve a commission from Latin America, Europe and the Middle East trying to reach a negotiated outcome between the Libyan leader and opposition forces which have seized control of large areas of the North African oil-producing country.
Moussa has confirmed that a Venezuelan peace plan is "under consideration".
In a resolution issued on Wednesday, the Arab League called on the Libyan government to respond to the "legitimate demands of the Libyan people" and to stop the bloodshed in the country.
Libya's membership of the organisation has been suspended in protest at the crackdown by pro-Gadaffi forces.
It also said it could impose a no-fly zone in co-ordination with the African Union if fighting continues.
But it has rejected calls for direct outside military intervention in Libya. Chavez is Gaddafi's main ally in Latin America. Both leaders regularly make public condemnations of US "imperialism" and have exchanged visits in recent years. He has said it would be hypocritical of him to join the chorus of international condemnation of Gaddafi.
Chavez posted a message on Twitter last week saying "Long live Libya and its independence! Gaddafii faces a civil war!"
He said on Monday he had discussed the idea of an international mediation effort with several Latin American and European countries.
"I hope we can create a commission that goes to Libya to talk with the government and the opposition leaders," he said. "We want a peaceful solution ... We support peace in the Arab world and in the whole world."
Without giving further details of the proposed mediation mission, Chavez said it was better to seek "a political solution instead of sending marines to Libya, and better to send a good will mission than for the killing to continue".
Al Jazeera's Dima Khatib, reporting from Caracas, said the comments come from "Chavez's ideology that the south can come up with solutions for the south".
"Chavez said that the door is open to all the 'friendly' nations," she said. "It will be interesting to see in the next few days, which countries will be willing to join this international peace commission."
"He says that this [condemnation] has been done against him [Chavez] in the past. He has been accused of harbouring al-Qaeda; he has been accused of all kinds of things without any proof," Al Jazeera's Khatib said.