Foreign Affairs Minister Chrystia Freeland will host the meeting that comes amid massive protests in Venezuela aimed at pressing the country's socialist leader, Nicolas Maduro, to vacate the presidency.
"We are in permanent contact with the governments of Spain, France, the United Kingdom and Germany".
Guaido's backers say he is the legitimate leader because he is president of Venezuela's congress, which they regard as the only lawfully elected power in the country.
"So UK alongside European allies now recognises Juan Guaido as interim constitutional president until credible elections can be held".
"I call on the Venezuelan people to sign ... at all the barracks, factories, schools", Maduro said.
Under Maduro's stewardship, oil-dependent Venezuela has plunged into an economic crisis, suffering from hyperinflation and shortages of food and medicine. A growing list of 38 countries has now recognized Guaido, including non-EU European nations Kosovo, Iceland and Albania.
In addition to the European pressure, a bloc of Latin American nations and Canada were to meet on Monday seeking to maintain pressure on President Maduro.
British Foreign Secretary Jeremy Hunt promptly followed suit, saying on Twitter he hoped "this takes us closer to ending humanitarian crisis". He also announced $53 million in humanitarian aid to support the Venezuelan people.
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 looking at what further steps we can take to ensure peace and democracy in Venezuela including through sanctions".
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"Individual EU Member States will acknowledge Mr. Juan Guaido, President of the National Assembly, as President ad interim of Venezuela", the proposed joint statement said, calling for "free, fair and democratic presidential elections". We did not participate, none of us, at the inauguration of Maduro on January 10.
Australia, Canada and Israel are among other countries to recognize him.
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.
Fourteen countries issued their own statements saying Guaido is now the country's legitimate leader, but others refused to follow suit on a decision that exposed how divided the European Union is on major global issues.
The Netherlands has joined the group of nations formally recognising Venezuelan opposition leader Juan Guaidó as the country's interim president.
The Government, it said, will "completely revise bilateral relations with those countries from now on".
The editor-in-chief of the Rossiya Segodnya International Information Agency Margarita Simonyan commented on Ottawa's refusal to grant accreditation to RIA Novosti and Sputnik, both part of Rossiya Segodnya, for the ministerial meeting of the Lima Group on Monday. In the past week, the leader has attended numerous exercises and spoken to soldiers, likely because of the major role the military will play in determining his future.
"The coward government of Spain has made a awful decision in the history of relations between Spain and Venezuela". You are making mistakes that will leave your hands covered in blood. Norway, not an European Union member, said it also was not recognising him. Already, the Bank of England has reportedly denied a request by Maduro to repatriate US$1.3 billion worth of Venezuelan gold being kept in its vaults.
He added: "No, global politics can't be based on ultimatums".