President Nicolas Maduro is attending the talks, which are being supervised by a Vatican envoy and other mediators.
Opposition is demanding a referendum be allowed to take place on whether Nicolas Maduro should step down.
For its part, the government wants the opposition to renounce violence and reject right-wing economic policies.
The meeting, at a museum in Caracas, follows a general strike and huge opposition rallies.
Nicolas Maduro shook hands with the five opposition leaders who including Jesus Torrealba, the leader of the Democratic Unity coalition.
Vatican envoy Archbishop Claudio Maria Celli urged both sides to engage in serious dialogue to defuse the mounting political crisis.
“The Pope is following the situation of this country very closely and hopes this process can continue peacefully,” he said.
Former political leaders from Spain, Panama and the Dominican Republic are also helping to mediate.
On October 28, opposition leaders in Venezuela organized a general strike to push for a referendum on removing President Nicolas Maduro from power.
Many shops, businesses and schools stayed closed but adherence to the strike was patchy and poorer areas largely ignored it.
Hundreds of thousands of people rallied against Nicolas Maduro on October 26, angered that a recall referendum process – an attempt to remove Maduro from power – had been suspended.
Opposition activists had gathered about 1.8 million signatures petitioning for the referendum, 400,000 of which were validated by electoral authorities.
Supporters of Nicolas Maduro have also taken to the streets.
The government and opposition are at loggerheads over Venezuela’s dire economic problems which have led to food shortages, lack of medical supplies and regular power cuts.
The inflation rate, already the world’s highest, is expected to spiral even further in 2017.
At least 158 people have died in Spain's worst flooding disaster in generations. On October…
Google has been fined two undecillion (a two followed by 36 zeroes) roubles by a…
Embarking on a home remodel is an exciting journey, promising enhanced comfort, increased property value,…
The US presidential candidates continued to campaign across key swing states on October 20. Footage…
Elon Musk has said he will give away $1 million a day to a registered…
India and Canada have decided to expel their top envoys along with other diplomats as…