The opposition group is made up of former lawmakers who were elected to the National Assembly in 2015, the last time opposition parties won a majority in the legislative body.
National Assembly elections held since then have either been boycotted by the opposition or widely dismissed as neither free nor fair, as Maduro and his PSUV party tightened their grip on all branches of government.
The opposition team will be led by Dinorah Figuera, who returned to Venezuela in June after almost eight years in exile.
Upon landing in Caracas, she told reporters that she had travelled to her home country “on invitation from the [US] State Department” with the aim of pushing for the renewal of the National Electoral Council (CNE).
The CNE has been dominated by staunch loyalists of the Maduro government for years.
It was CNE which declared Maduro the winner of the 2024 presidential election even though voting tallies gathered by electoral observers and verified independently showed an overwhelming victory for the opposition candidate, Edmundo González.
In its statement, released on Tuesday, the opposition group said that the priority of the talks would be the strengthening of the democratic institutions and the electoral system, as well as providing guarantees for political participation.
Opposition politicians and those who have expressed criticism of the Maduro government have for years faced persecution.
Many have been jailed and many others have fled into exile.
Despite the release of scores of political prisoners following the ouster of Maduro, 372 remain behind bars, according to a tally by prisoners’ rights group, Foro Penal.
The best-known opposition leader, María Corina Machado, has not yet been able to return to Venezuela after slipping out of the country secretly in November to receive the Nobel Peace Prize for her work promoting democracy.
Despite dedicating her Nobel Prize to US President Donald Trump, his administration now seems to favour Dinorah Figuera over Machado as the person to negotiate a democratic transition in Venezuela.
Machado tried to return to Venezuela shortly after the twin earthquakes but failed to make it into the country.
And while President Trump has denied that his administration blocked her efforts to enter Venezuela, US media had earlier quoted unnamed officials as describing her attempts to return as “potentially disruptive” to the post-earthquake rescue and reconstruction efforts.
Machado has not yet commented on the announcement of the talks but called on the coalition of opposition parties she leads to meet later on Wednesday to discuss it.