Speaking to AFP via voice notes sent while in hiding amid fears for her safety, Maria Corina Machado also called for greater support from the international community for Venezuela's political opposition, which is disputing Maduro's July 28 election victory.
Her responses came as Maduro is set to appear before Venezuela's Supreme Court on Friday, as he asks the top judicial body to affirm his reelection.
"We are determined to move forward in a negotiation," said Machado, 56. "It will be a complex, delicate transition process, in which we are going to unite the whole nation."
Venezuela has been in crisis since election authorities declared Maduro the winner of last month's poll, a decision questioned by the opposition and much of the international community.
The National Electoral Council (CNE), which declared Maduro the winner with 52 percent of the vote, has yet to release detailed results.
The opposition meanwhile has launched a website with copies of 84 percent of ballots cast, showing an easy win for their candidate, Edmundo Gonzalez Urrutia. The government says those results are forged.
"Maduro completely, absolutely, lost legitimacy," Machado told AFP. "All Venezuelans and the world know that Edmundo Gonzalez won in a landslide."
"I feel deeply proud of what we have done, of what Venezuelan society has done, overcoming all obstacles in the most unequal and arbitrary election," she added.
Machado won opposition primaries to face Maduro in October 2023, but was barred by authorities from running.
In her place in the general election was taken by 74-year-old Gonzalez Urrutia.
"We are a team," said Machado, who campaigned for the little-known diplomat and remains the highest-profile opposition leader.
Gonzalez Urrutia has not appeared in public for more than a week during a crackdown on protesters by Maduro's government.
Demonstrations sparked last week by the declaration of Maduro's victory left at least 24 people dead, according to rights groups, with thousands also arrested.
Much of the international community, from the United States to left-wing Brazil, Colombia and Mexico have scrutinized the vote results.
"It is time for all the governments of the world to raise their voices against repression and recognize the victory of Edmundo Gonzalez... and at the same time make Maduro understand that his best option is a negotiated transition," Machado said.
She added that the military leaders who have declared their loyalty to Maduro "do not represent the aspiration of the immense majority of our national armed forces."
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