Henrique Capriles, a top figure in the opposition MUD coalition, said the announcement of talks was a ploy Maduro.
Henrique Capriles, a top figure in the opposition MUD coalition, said the announcement of talks was a ploy by President Nicolas Maduro to keep resisting the opposition's efforts to remove him from power.
Vatican envoy Emil Paul Tscherrig said earlier in Caracas that the sides had agreed to start a formal dialogue on October 30 with a view to resolving the crisis.
His announcement came after Maduro had a private audience at the Vatican with the pope.
It raised hopes of resolving a worsening crisis in the volatile country, stricken by food shortages.
But Capriles said Maduro was seeking to defuse the pressure after the opposition accused him of staging a coup d'etat by blocking its bid for a vote on removing him.
"What dialogue? No dialogue has been started in Venezuela," Capriles said in an address broadcast online.
Maduro's side "is trying to use Pope Francis's good faith and the good faith of the Vatican envoy... to say: nothing has gone wrong here," he alleged. "Rest assured the opposition will never go along with that."
And "a meeting on Margarita (island) was never discussed. I heard about it on TV," Capriles said.
Months of tension that have included riots and looting were threatening to boil over after authorities enraged the opposition last week by annulling its drive for a recall referendum.
Rulings by the courts and electoral authorities have blocked the opposition's efforts for a referendum this year.
Under constitutional rules, if a referendum is not held by January 10, Maduro could just hand power to his vice-president if he lost the vote.
The opposition members who hold a majority in the legislature had vowed to debate on Tuesday whether to mount a "political trial" against the president.
They also vowed massive nationwide street protests on Wednesday.