The coordinated move from major European nations came after the expiry of an eight-day deadline they set last weekend for President Nicolas Maduro to call a new vote.
The Venezuelan leader, accused of running the OPEC nation like a dictatorship and wrecking its economy, has defied that, saying Europe’s ruling elite are sycophantically following US President Donald Trump’s agenda.
Guaido, who leads the opposition-controlled National Assembly, declared himself temporary leader last month in a move that has split global powers.
Trump immediately recognised him and European Union nations back Guaido, though some have been nervous over the global precedent of a self-declaration.
Russia and China, who have poured billions of dollars of investment and loans into the OPEC nation, are supporting Maduro.
“I recognise the president of Venezuela’s assembly, Mr Juan Guaido, as president in charge of Venezuela,” Spanish Prime Minister Pedro Sanchez said in a televised statement, urging a free and fair election as soon as possible.
British Foreign Secretary Jeremy Hunt followed suit.
“Nicolas Maduro has not called presidential elections within 8-day limit we have set,” Hunt said on Twitter. “So UK alongside European allies now recognises @jguaido as interim constitutional president until credible elections can be held.”
French Foreign Minister Jean-Yves Le Drian told France Inter radio station Guaido has “the capacity and the legitimacy” to organise a presidential election.
Le Drian said France would consult European partners over Venezuela, and that it was imperative the conflict was resolved peacefully and civil war avoided.
Sweden, Austria and Denmark also said they recognised Guaido as interim leader of Venezuela.
Maduro, 56, a former union leader, bus driver and foreign leader, replaced former leader Hugo Chavez in 2013 after his death from cancer. But he has presided over an economic collapse and exodus of 3 million Venezuelans.
He blames a US-led “economic war” and also accuses Washington of seeking a coup against him. But critics say incompetent policies and corruption have gutted a once-wealthy nation while dissent has been brutally crushed.
Russia said the coordinated European move was an attempt to legitimise Guaido’s illegal attempt to seize power and amounted to foreign meddling.