The UK, France, Germany, Spain and other European countries have officially recognised opposition leader Juan Guaidó as interim president of Venezuela.
It comes after President Nicolás Maduro defiantly rejected the EU's Sunday deadline to call snap elections.
Mr Guaidó declared himself interim leader last month and won US backing.
Russia - a backer of Mr Maduro - accused EU countries of meddling in Venezuela's affairs.
As pressure mounted on Mr Maduro to step down, he said he could not rule out the possibility of civil war.
In a TV interview, he warned that US President Donald Trump would leave the White House "stained with blood" if he intervened in the crisis.
Mr Guaidó said on Sunday he would build an international coalition to deliver humanitarian aid to Venezuelans.
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