France, Germany, Britain and Spain had given Maduro until midnight on Sunday to call a presidential election, failing which they would recognise opposition leader Juan Guaido as the interim president.
But in an interview with Spanish TV station Sexta Maduro said that he would not "cave in to pressure" from those calling for his departure.
"Why does the European Union have to tell a country in the world that has already had elections that it has to repeat its presidential elections, because they were not won by their right-wing allies," said Maduro, interviewed in Caracas.
"They are trying to corner us with ultimatums to force us into an extreme situation of confrontation," Maduro said.
When asked if the crisis in Venezuela could result in civil war he replied “no-one could answer that question with certainty” warning that US President Donald Trump would leave the White House “stained with blood” if he were to intervene in the crisis.
French-backed ultimatum rejected
Earlier on Sunday, France's European Affairs Minister Nathalie Loiseau had said European nations would join the US and others in recognising Juan Guaido, the 35-year-old National Assembly head who declared himself acting president last month and won US backing, as legitimate leader.
"The ultimatum ends tonight," she told French media.
Loiseau added that Maduro's suggestion of bringing forward parliamentary elections scheduled for 2020 was "a farce, a tragic farce".
Trump says sending military ‘an option’
US President Donald Trump has said that sending the military to Venezuela was "an option" and that he had turned down Maduro's request for a meeting.
"Certainly, it's something that's on the... it's an option," Trump said in an interview with CBS broadcast on Sunday.
But Maduro warned the US leader he risked a repeat of the Vietnam War if he intervened.
"Let's respect each other, or is it that you are going to repeat a Vietnam in Latin America?" he said.
The European Union says that a newly formed "International Contact Group" of European and Latin American countries will hold its first meeting in Uruguay on Thursday to address the Venezuela crisis.
A joint statement from EU foreign policy chief Federica Mogherini and Uruguayan President Tabare Vazquez on Sunday said that the meeting in Montevideo will be held at ministerial level.
The contact group includes the EU and eight of its member countries – France, Germany, Italy, the Netherlands, Portugal, Spain, Sweden and Britain, as well as Latin American nations Bolivia, Costa Rica, Ecuador and Uruguay.
Its stated aim is "contributing to create conditions for a political and peaceful process to emerge, enabling Venezuelans to determine their own future" through free and credible elections.
Juan Guaido said on Sunday he would build an international coalition to deliver humanitarian aid to Venezuelans but Maduro has accused him of organising a coup.
The Venezuelan president has overseen an economic collapse and the exodus of millions of Venezuelans, but still has the powerful backing of Russia, China and Turkey, and the critical support of the military.