France, Spain, Sweden and the United Kingdom announced Monday that they were recognizing opposition leader Juan Guaido as Venezuela's interim president after an eight-day deadline for Maduro to call elections had not been met.
Spain, Germany, France and Britain delivered diplomatic blows to Maduro's rule by publicly supporting Guaido after a Sunday deadline for Maduro to call a presidential election passed without action.
But Italy blocked the draft European Union statement.
Spanish Prime Minister Pedro Sanchez was another leading political figure to endorse Guaido as interim president, while also urging him to call an election in the near future.
Asked in Brussels on Monday whether Ireland would follow other major European Union nations in recognising him, Ireland's Foreign Minister Simon Coveney told reporters: "No, our position has been clear".
In Sweden, Foreign Minister Margot Wallstrom said the election that brought Maduro to power was neither free nor fair and told Swedish SVT that Venezuelans "now must get new, free and fair elections instead".
Since then, he has been courting the worldwide community - including Maduro's staunchest supporters, Russian Federation and China - as well as Venezuela's military leaders.
World powers are taking sides in the deadly struggle to lead Venezuela, which has pitted some Western nations against Russia, China and others.
Long-time backers Russian Federation and China are among at least nine nations that have declared their support for Maduro.
"The oppression of the illegitimate, kleptocratic Maduro regime must end".
"Soldiers of the fatherland: We need the humanitarian aid to come, for your mother, your sister and all your family", Guaido said at a news conference at the National Assembly to thank the European governments for their support.
President Maduro also had choice words for Washington's transatlantic allies, describing Europe's ultimatum to hold new elections as "the stuff of empires, of colonial times".
"We are not beggars", Maduro said on Venezuelan state TV.
Opposition leader and self-proclaimed "acting president" Juan Guaido, center, chants slogans as he marches with students during a protest he convened against the government of President Nicolas Maduro, outside Venezuela's Central University (UCV) in Caracas, on January 30, 2019.
The 14-nation so-called Lima Group, which includes Canada and Latin American countries such as Brazil and Mexico but not the United States, met in Ottawa to discuss the way forward on Venezuela.
Guaido is expected to announce a date for the arrival of humanitarian aid from the USA - a path Maduro believes will lead to a US-led military intervention.
The 35-year-old lawmaker, who is the head of the South American country's National Assembly, declared himself Venezuela's interim head of state last month, directly challenging Maduro's claim to the presidency. The European Parliament has called on all EU countries to do so.
All eyes are now on Venezuela's military, which has so far been Maduro's main pillar of support, but there have been signs of unrest in the ranks.
He added that "no one imposes an ultimatum on Venezuela".
If all European countries follow in the footsteps of the Trump Administration, their decision to recognise Guaido could potentially cut the Venezuelan Government off from any accounts or assets in those countries.