"We have arrived at Barbados to continue peace dialogue. Together with Pope Francis, we hope that we will all strive to build a peaceful dispute resolution mechanism and stop aggression against our people", Rodriguez wrote on Twitter.
According to the ministry, the government delegation includes, among others, foreign minister Jorge Arreaza as well as Hector Rodriguez, the governor of the state of Miranda.
Earlier, representatives of US-backed opposition leader Juan Guaido, who declared himself interim president of Venezuela, reported on the participation of his delegation in the new round of talks in Barbados.
On 12 July, Rodriguez said that the Venezuelan government and the opposition had agreed to engage in a permanent peace dialogue as a result of three-day talks that took place in Barbados in the first week of July.
Venezuela is experiencing a political and economic crisis that intensified in January after Guaido proclaimed himself interim president.
The US soon began imposing sanctions on Venezuela and froze billions of dollars’ worth of Venezuelan assets.
The country's president, Nicolas Maduro, has called Guaido a US puppet and accused the US of orchestrating a coup in Venezuela to force a change of government and claim the country’s vast fossil fuel reserves, the largest in the world.
Dozens of countries have endorsed Guaido, and called on Maduro to step down, and for a new election to be organized. China, Russia, Turkey and numerous others have, in turn, voiced their support for constitutionally-elected Maduro as Venezuela's legitimate president.
Since May, two rounds of talks between Maduro's representatives and the opposition have been held in Oslo with Norway's mediation.