Maduro's latest comments, which came via interviews and a video posted online, arrived just ahead of planned street demonstrations by the nation's opposition on Wednesday and amid new threats via US national security advisor John Bolton who continues to lead the charge for regime change on behalf of the Trump administration.
Trump and Guaido spoke by telephone on Wednesday.
On Wednesday, Maduro rejected calls for a snap presidential election as blackmail, and reiterated he was ready for talks with the opposition and possible third country mediation, Russia's RIA news agency reported.
Under Venezuela's constitution, the head of the National Assembly is empowered to take on the duties of the chief executive under a range of circumstances in which the presidency is vacated.
"The military's withdrawal of support from Mr. (President Nicolas) Maduro is crucial to enabling a change in government". He has been recognized by the United States and other major countries as Venezuela's interim leader.
The showdown in Venezuela once again playing out in the streets. The declaration came less than two weeks after Maduro, who won re-election in a vote the opposition called illegitimate, was sworn into office for his second presidential term.
President Trump also noted in his tweet that Guaido "is being targeted by Venezuelan Supreme Court", a reference to a request by the country's attorney general, Tarek William Saab, for the high court to prevent Guaido from leaving the country and block his financial accounts.
On Tuesday Trump's National Security Advisor John Bolton was photographed holding a note stating "5,000 troops to Columbia".
This decision had been taken as part of a deal reached by the Lima Group aimed at countering the Venezuelan government, the official added, as cited by the Republic news outlet on Wednesday.
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"Venezuela has risen up to dream of the country we want to be", said Guaido.
The US slapped oil sanctions on Maduro's regime earlier this week in an attempt to starve the government of its funding. "If the USA intends to invade us, they will have a Vietnam worse than they can imagine". But any money Citgo earns will be placed in a blocked account.
"I ask for the support of the people of the United States so that there is not a new Vietnam", he said in the video posted on Facebook.
Treasury Secretary Steven Mnuchin said Venezuela can get relief from the sanctions when control of the oil company is turned over to Guaido.
Since 2012, fuel supply failures have been chronic in the cities of San Cristobal and Maracaibo, near the border with Colombia, with unending queues of vehicles at petrol stations.
And the prospect of the U.S. using force to oust Mr Maduro increased after White House national security adviser John Bolton was seen on TV holding a notepad containing the note "5,000 troops to Colombia", which neighbours Venezuela.
Maduro, in response, announced the severing of diplomatic and political ties with the United States.
Maduro, 56, accused Trump of ordering his assassination, while his main global backer Russian Federation called Wednesday for mediation in a standoff that is splitting foreign powers.
He has called world leaders who want him gone "Trump sycophants".