The Netherlands has joined the group of nations formally recognising Venezuelan opposition leader Juan Guaidó as the country's interim president.
But with the majority of the military still standing with Maduro, is the country stumbling towards civil war?
Seven EU states had given Maduro a Sunday midnight deadline to call presidential elections or they would recognise Guaido.
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.
"From today, we will spare no effort in helping all Venezuelans achieve freedom, prosperity and harmony", Spanish Prime Minister Pedro Sanchez said, urging both fair elections and humanitarian aid.
He said Spain, which has a sizable Venezuelan community, also is working on a humanitarian aid program for Venezuela, where shortages of basic items are acute.
British Prime Minister Theresa May's spokesman, James Slack, said Britain is considering imposing sanctions to help bring about change in Venezuela.
The words of the European politicians were followed by German Chancellor Angela Merkel confirming her support for Guaido.
Earlier French Foreign Minister told French radio that Guaido had the right to call snap elections.
"This is a pivotal moment for the people of Venezuela - we are observing a widespread rejection of the Maduro regime's illegitimate claim to power following fraudulent elections last May", he said.
U.S. President Donald Trump said military intervention in Venezuela was "an option" as Western nations boost pressure on socialist leader Nicolas Maduro to step down, while the troubled OPEC nation's ally Russian Federation warned against "destructive meddling". "It is, definitely, the people of Venezuela who have to decide its future".
Subsequently, Venezuela's incumbent President Nicolas Maduro blasted these actions as an attempted coup and said he was cutting diplomatic ties with the United States. "I hope we will have a positive answer [from him]", Maduro told Italian news channel SkyTg24.
Last week, the EU's top diplomat sounded a warning about the outlook for Venezuela amid the political standoff in the country.
Maduro and Guaido have been battling for legitimacy in a struggle that has drawn in the world's major powers on one side or the other.
The embattled president on Sunday promised peace for Venezuela without specifically responding to Trump.
"The United States wants to return to the 20th century of military coups, subordinate puppet governments and the looting of resources", he said, adding Trump would leave the White House "stained with blood" if there is a military intervention.
But its statement was more measured than that of CUPE, focusing on calling for the government to "promote dialogue to foster a peaceful solution to the Venezuelan crisis".
The worldwide pressure on Venezuelan leader Maduro intensified on Monday as a host of European Union nations declared his rival Guaido as interim president. It aims to facilitate dialogue and is due to hold its first meeting in Uruguay on Thursday. But sources say Canada won't be adding to the humanitarian fund because Maduro won't allow proper humanitarian access into the country.
Tens of thousands of Venezuelans have turned out in recent protests to demand Maduro's exit, although he appears to have the support of the nation's powerful military and security services.