Protests have been held in recent days over the suspension of a referendum process seeking to remove President Nicolas Maduro.
The move came after Nicolas Maduro met Pope Francis in an unannounced visit.
The Vatican and regional bloc Unasur will mediate in the talks.
Pope Francis “urged [the parties] to show courage in pursuing the path of sincere and constructive dialogue”, the Vatican said in a statement.
After meeting representatives from both sides, the Vatican’s envoy to Argentina, Emil Paul Tscherrig, said “a national dialogue” had already started.
He said they had agreed to formal talks on Sunday on Margarita island in the Caribbean.
Nicolas Maduro said “at last” dialogue could begin.
The head of the opposition coalition, Jesus Torrealba, who met Emil Paul Tscherrig, said while talks were important “it can’t continue to be a strategy for the government to win time”.
Another top opposition figure, Henrique Capriles, dismissed the announcement as a diversionary ploy.
“No dialogue has begun in Venezuela,” he said.
Nicolas Maduro, a former bus driver and union leader, is blamed by the opposition for Venezuela’s dire economic situation. The oil-rich country is facing widespread food shortages and spiraling inflation.
The opposition is trying to hold a recall referendum that would allow Nicolas Maduro to be removed from office but electoral authorities suspended the process last week.
The official reason was allegations of fraud during the gathering of signatures for the first petition required to enable the referendum.
However, opposition lawmakers have long accused the National Electoral Council of being under the government’s control.
In an emergency session of the National Assembly on October 23, they approved a resolution accusing Nicolas Maduro’s Socialist government of engaging in “an ongoing coup d’etat”.
The Organization of American States also said it was “profoundly worried” by the electoral authorities’ decision.
Hundreds of students protested on October 24 in San Cristobal, a city near the Colombian border. Nationwide protests are planned for October 26.
Nicolas Maduro has accused the opposition of having links to foreign states, the US in particular, and of seeking to overthrow him to “lay their hands on Venezuela’s oil riches”.
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