Maduro made the surprise announcement in a televised cabinet meeting in Caracas.
He told his ministers he would accept to undertake talks brokered by Dominican Republic President Danilo Medina and ex-Spanish premier Jose Luis Rodriguez Zapatero.
“Zapatero and President Medina know very well that I have been a promoter of this dialogue and I accept this new day of dialogue,” Maduro said.
Maduro appointed influential Caracas politician Jorge Rodriguez as his representative at the talks, and said he would leave for the Dominican Republic.
The opposition announced in turn that it would hold an exploratory meeting with the Dominican president.
However, it insisted it did not mean it was the beginning of formal talks with the government.
“The time for symbolic gestures is over,” the opposition coalition Democratic Unity Roundtable said. “To enter into serious negotiation, we demand immediate actions that demonstrate a real willingness to resolve the national problems and not to win time,” it said.
Oil-rich Venezuela is facing a growing economic crisis that has caused shortages of food and medicine as it faces the prospect of default to its Russian and Chinese creditors.
Maduro had to weather falling oil prices and a wave of opposition protests that left 125 people dead between April and July.
Medina and Zapatero will hope their efforts to find a solution in Venezuela are more fruitful than those of the Vatican and the Union of South American Nations who brokered the last meeting between the two sides in October last year.
Those talks broke up a month later with the opposition accusing the government of failing to adhere to earlier agreements to free political prisoners and prepare elections.
United Nations secretary-general Antonio Guterres expressed his “full support” for the initiative, stressing that the Venezuelan crisis requires a “political solution based on dialogue.”
International powers accuse Maduro of dismantling democracy by taking over state institutions in order to resist opposition pressure for him to quit, amid an economic crisis that has caused shortages of food and medicine.
