The coordinated recognition by a flood of European Union nations including Britain, Germany, France and Spain followed the expiration of an ultimatum for Maduro to call a new presidential election, aligning them with Washington and against Russian Federation and China.
France, Germany, Portugal, Austria, Sweden, Denmark, Latvia, Lithuania, Finland and the Netherlands also recognized Guaido.
"So UK alongside European allies now recognises Juan Guaido as interim constitutional president until credible elections can be held".
Swedish Foreign Minister Margot Wallstrom said the election that brought Maduro to power was neither free nor fair and told Swedish broadcaster SVT on Monday that Venezuelans "now must get new, free and fair elections instead".
Spain's Prime Minister Pedro Sanchez delivers a statement at the Moncloa Palace in Madrid, Spain, Monday, Feb. 4, 2019.
It is unclear whether Maduro's government, which denies the country is suffering a humanitarian crisis, will let any foreign aid through.
Venezuela has as many as 2,000 generals, according to unofficial estimates, many of whom do not command troops and whose defection would not necessarily weaken the ruling socialists.
Italy, however, blocked a joint European Union position to recognise Guaido as interim president, diplomatic sources said, with the government in Rome deeply divided over the issue.
"Venezuela has to be the master of its own destiny, and it is up to the worldwide community to help and respect the outcome of the democratic process and verify that it takes place with all necessary guarantees", he said.
"The people of Venezuela have suffered enough".
National President of the Canadian Union of Postal Workers Mike Palecek said the protesters wanted to send a message that Canada should not interfere in a foreign democracy. "Venezuelans have the right to express themselves freely and democratically", he wrote on Twitter.
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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.
"Therefore, Guaido is the person we are talking to and we expect him to begin an election process as soon as possible".
A spokesman for Prime Minister Theresa May said the United Kingdom was looking at options to help expedite peace and democracy in Venezuela, including the use of sanctions.
"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.We did not participate, none of us, at the inauguration of Maduro on January 10.
The US and other countries have already pledged humanitarian aid for Guaido's administration, though it remains to be seen where and how it can enter the country without the military's support.
Some of the EU countries backing Guaido are part of a newly formed "International Contact Group" of eight European and four Latin American nations.
"The people will never surrender", the embattled Venezuelan president Nicolas Maduro has declared as he condemned what he called the "cowardly" and "disastrous" move by Britain and other European countries to recognise his opponent Juan Guaidó as interim president.
Meanwhile, in Canada, foreign ministers from Western hemisphere nations belonging to the Lima Group, which includes 13 countries that took the lead in recognizing Guaido as Venezuela's rightful leader, gathered in Ottawa to discuss additional steps to pressure Maduro.
The Government, it said, will "completely revise bilateral relations with those countries from now on".
Mexico and Uruguay have not recognized Guaido, the head of the National Assembly who declared himself acting president on January 23 in place of Maduro. 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.