People took to the streets in the capital Caracas and various other cities, banging pots, blowing whistles and horns, and carrying banners that read: "Armed forces, regain your dignity," "Maduro usurper," "Guaido, president" and "No to the dictatorship."
"Don't shoot people who are making demands also for your family," Guaido said in a message to the military delivered from the central university in Caracas.
The man challenging Maduro's claim to the presidency had urged Venezuelans to step outside their homes and workplaces for two hours beginning at noon in the first mass mobilisation since he declared himself the nation's rightful leader a week ago during another round of big protests.
"Venezuela is set on change," Guaido said.
The surge in political maneuvering has seen two dozen nations, including the US and several Latin American countries back Guaido. The Trump administration has imposed sanctions that could starve the already distressed nation of billions in oil revenue.
"Large protests all across Venezuela today against Maduro. The fight for freedom has begun!" US President Donald Trump tweeted Wednesday after speaking with Guaido.
France said on Wednesday that Maduro appeared not to be heeding calls for new presidential elections and that European foreign ministers would discuss next steps in Bucharest on Thursday.
Along with other EU members, France has said it would recognise Guaido as the country's rightful leader if Maduro failed to call a new vote within eight days.
‘Vietnam in Latin America’: Maduro
But Maduro is holding firm and refusing to step down. He huddled with military troops early Wednesday and has overseen military exercises in recent days while seeking to consolidate support from the armed forces.
In an interview with FRANCE 24 Tuesday, Guaido said he plans to reach out to the country's powerful armed forces and appeal to them to help "build a democracy, rebuild our country and ensure a transition government”.
Maduro however has accused Washington of staging a coup and pressed his case directly to the American people in a short video shot in the presidential palace. US President Donald Trump and "this group of extremists" have their eyes on Venezuela's vast oil reserves, said Maduro, warning that the US is about to repeat a bloody chapter in its history.
"We won't allow a Vietnam in Latin America," Maduro said. "If the aim of the United States is to invade, they'll have a Vietnam worse than can be imagined."
In an interview with Russia's state-owned RIA Novosti news agency on Wednesday, Maduro said he was "willing to sit down for talks with the opposition for the sake of Venezuela's peace and its future... It would be very good to conduct parliamentary elections at an earlier stage."
The opposition however rejected his offer, citing many instances in the past when Maduro has simply talked about talks to try to defuse a crisis situation.
France on Wednesday said Maduro had not responded to an EU demand for elections.
Russia is one of the staunchest supporters of Maduro and has offered to mediate in the crisis.
Top court bars Guaido from leaving Venezuela
On Tuesday, the Supreme Court barred Guaido from leaving the country after chief prosecutor Tarek William Saab announced that he was opening a criminal investigation of Maduro's foe, who heads the opposition-controlled congress. Saab is a key Maduro ally and the high court is stacked with Maduro loyalists.
The court move came after US National Security Adviser John Bolton warned that the Maduro government would face "serious consequences" if Guaido is harmed.
Guaido has thus far managed to avoid arrest and the Supreme Court did not strip him of his legislative immunity, though the new investigation could signal that Maduro's administration is moving to take a more punitive approach.
Speaking Tuesday outside the National Assembly, Guaido said he was aware of personal risks.
"I don't underestimate the threat of persecution at the moment, but here we are," he said.
Guaido gets control of Venezuela’s US bank accounts
The US has emerged as Guaido's most powerful ally, announcing on Tuesday that it was giving him control of Venezuela's US bank accounts.
US Secretary of State Mike Pompeo certified that Guaido has the authority to take control of any Venezuelan government accounts at the Federal Reserve Bank of New York or any other US-insured banks. He said the certification would "help Venezuela's legitimate government safeguard those assets for the benefit of the Venezuelan people".
The US on Monday imposed sanctions on Venezuela's state-owned oil company, Petroleos de Venezuela SA (PDVSA), that could potentially deprive the Maduro government of $11 billion in export revenues over the next year.
On Wednesday, Bolton announced that Washington had sanctioned Nicaragua's Albanisa, a private company that imports and sells Venezuelan petroleum products.
"Through sanctioning PdVSA, the United States has also sanctioned Nicaragua's ALBANISA, the government's joint venture with PdVSA and slush fund of the corrupt regime of Daniel Ortega," said Bolton in a tweet.
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