The opposition is vowing to deliver on Saturday large amounts of US -supplied aid warehoused in the Colombian border city of Cucuta, despite orders from Maduro to his armed forces to block their plans.
Under Mr Maduro's orders, Venezuela this week blocked air and sea travel between Venezuela and the nearby Dutch Caribbean island of Curacao, another point where aid was being stockpiled.
Embattled Maduro has dismissed Guaido's humanitarian caravan as a "cheap show" and insisted aid is a precursor for a U.S. military intervention in the oil-rich but economically crippled Latin American country. Crowds formed alongside a main highway out of the capital, waving Venezuelan flags and whooping in support.
Lawmakers said Guaido's vehicle continued but his exact location was being kept a secret due to security concerns.
Opposition leaders said they also plan to bring emergency supplies of food and medicine from Curacao and across the jungle-covered border with Brazil.
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Maduro accuses the Trump administration, which recognizes Guaido and has levied crippling sanctions against the Venezuelan government, of seeking to force his ouster.
Fifty countries, including Germany, have recognized Guaido as interim president since he openly challenged Maduro.
Mr Guaido is backed by the USA and dozens of nations, while Mr Maduro is supported by Russia, China, Cuba, Turkey and many other countries.
But Brazilian Vice President Hamilton Mourao dismissed U.S. threats of military intervention in Venezuela as "premature" and said it "wouldn't make sense".
"The struggle in Venezuela is between dictatorship and democracy, and freedom has the momentum". Maduro was sworn in for a second term, but Guaido declared himself the rightful leader since the country's constitution permits him to assume temporary power when the president is deemed illegitimate.