He did not specify a date for resumption of the talks at the new venue, in the Caribbean, after earlier discussions were stalled in Norway.
“In response to the mediation of the Kingdom of Norway (the opposition) will attend a meeting with representatives of the usurper regime in Barbados, to establish a negotiation on the end of the dictatorship,” Guaido said in a statement.
Delegations representing the Venezuelan rivals met face-to-face in Oslo for the first time in late May, in a process that began two weeks earlier under Norwegian auspices to find a solution to the South American country’s economic and political crises.
Oil-rich Venezuela has been ravaged by five years of recession marked by shortages of food, medicine and other basic necessities.
It plunged deeper into political turmoil in January when National Assembly speaker Guaido declared himself acting president in a direct challenge to Maduro’s authority.
Last Tuesday Guaido had said there were no plans to reopen talks with the “murderous dictatorship” of Maduro, following the death of an officer in custody over an alleged coup plot.
The suspicious death of retired naval officer Rafael Acosta Arevalo sparked international condemnation.
Guaido said at that time, though, that if fresh talks aimed at “facilitating the cessation of the usurpation” of Maduro were announced, “we will officially communicate.”
The Barbados talks will be the third round since May.
Guaido wants them to lead towards Maduro’s departure from the presidency he has held since 2013, to a transitional government, and then to “free elections with international observers”.
Maduro has repeatedly said that the dialogue “will continue” with the opposition, “for peace in Venezuela.”
During a parade last Friday celebrating the country’s independence, Maduro said there would be “good news” this week about the negotiations.
Venezuela is suffering from hyperinflation in an economic crisis that has forced millions to flee. The United Nations estimates that more than seven million Venezuelans are in need of urgent humanitarian aid.
But Maduro has withstood a US-led pressure campaign that includes sanctions on Venezuela’s crucial oil exports.