The meeting, brokered by foreign ministers from the Unasur bloc of South American governments, took place at the Miraflores presidential palace in Caracas and was broadcast live on TV.
"The road here was long and complicated, but it was worth it ... we are going to listen patiently, and with respect and tolerance, to the compatriots of the opposition," Maduro said in lengthy opening comments.
He cautioned against unrealistic expectations.
"There are no negotiations here. No pacts. All we're looking for is a model of peaceful coexistence, of mutual tolerance."
Some opposition groups, including the party of jailed protest leader Leopoldo Lopez, boycotted the talks while dozens of demonstrators remain in jail.
Protests broke out in the capital as the talks were taking place.
Al Jazeera's Mariana Sanchez, reporting from Caracas, said demonstrators were saying that the only way to overcome the crisis is removing Maduro from office.
"Protesters are in no mood to negotiate," she said.