Maduro was sworn in on Thursday for a second term following a disputed 2018 election, triggering a hailstorm of global criticism that his leadership of the country suffering a hyperinflationary collapse is illegitimate.
Opposition leaders have faced significant hurdles in recruiting military dissidents due to Maduro's continued sway over the armed forces and a crackdown on accused insurgents that human rights groups have said includes torture of officers and abuse of their families. Prisons Minister Iris Varela appeared to threaten to jail him, although she has previously threatened other opposition members who remain free.
"I hope you quickly name your cabinet to know who is going to accompany you", Varela said.
The country's constitution says a presidential vacancy can be filled by the head of the legislature, and some opposition activists have called on Guaido to assume the presidency.
The head of the Organization of American States, Secretary-General Luis Almagro, wasn't waiting.
US national security adviser John Bolton then praised Guaido, athough he didn't echo Almagro's step of calling him the interim president.
Guaido asked Venezuelans to mass in a nationwide demonstration on January 23, a historically important date for Venezuelans - the day when a mass uprising overthrew dictator Marcos Perez Jimenez in 1958.
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We commend the courage of the National Assembly's leadership, particularly its president, Juan Guaido, and his decision to invoke the authorities of the Venezuelan Constitution.
Having lost control of parliament in 2016, Maduro a year ago created a rival Constituent Assembly filled with loyalists while his allies at the Supreme Court stripped parliament of its powers.
At a ceremony Thursday, Maduro was sworn in by Venezuela's Supreme Court before a group of pro-government supporters.
The hand-picked successor to late strongman Hugo Chaves also has the backing of the military high command, which reiterated its "loyalty" to the president on both Wednesday and Thursday. Maduro won re-election previous year despite hyperinflation, chronic food shortages, and a severe economic crisis.
"The Maduro regime is illegitimate and the United States will work diligently to restore a real democracy to that country", Pompeo told reporters on Saturday in Abu Dhabi during his tour of the Middle East countries. "We are very hopeful that we can be force for good to allow the region to come together to deliver that".
"The United States government will continue to use the full weight of US economic and diplomatic power to press for the restoration of democracy in Venezuela", he said in the statement, released in Abu Dhabi where Secretary of State Mike Pompeo was visiting as part of a Mideast trip.