Israel is among USA -aligned powers that rallied to Guaido after he declared himself Venezuela's leader last month in a power struggle with socialist President Nicolas Maduro, under whom the country has sunk into poverty.
"It's sure that the humanitarian aid will enter Venezuela because the usurper will have no choice but to leave Venezuela", said Guaido, referring to Maduro, whom he deems illegitimate over his reelection a year ago in a poll widely viewed as fraudulent.
Venezuela's economic crisis has left people from all walks of life struggling for food, basic living essentials and medicine.
At some point in the crisis, Washington also slapped sanctions on the state oil company, PDVSA, and its U.S. subsidiary Citgo.
The US is sparking a war to seize Venezuela, he said, highlighting that "Venezuela is a country that has the capacity to satisfy all the necessities of our people" and that "our people do not to beg from anyone".
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The rallies occurred almost three weeks to the day that opposition leader Juan Guaido invoked a constitutional provision to assume the presidency, arguing that Maduro's re-election past year was a sham.
"Here is a direct order to the armed forces: allow in the humanitarian aid once and for all (and) end the repression", said Guaido, 35, who stunned the world on January 23 when he launched his challenge to Maduro's authority by declaring himself acting president.
"It's a political war of the United States empire", Maduro said in the interview, "of the interests of the extreme right that today is governing - of the Ku Klux Klan - that rules the White House, to take over Venezuela". One bore a wooden cross to symbolize how Maduro was "crucifying the Venezuelans", he said.
Many European countries and the U.S. have recognised Guaido as the legitimate president, but Maduro is backed by Russia, China, and Venezuela's military.
In Caracas on Tuesday, a sea of colors gathered downtown as thousands emerged to share in the carnival atmosphere. "We are waiting for humanitarian aid to see if this medicine arrives", he said. "With that we could solve our country's problems".
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Maduro, who has come under intense internal and global pressure to hold free and fair elections as the crisis escalates, has refused to accept assistance, claiming it's a Trump administration ploy to take over his country.
But the military has barricaded a border bridge linking the countries, with Maduro describing the aid as a "political show" and a pretext to a United States intervention.
Guaido is trying to oust Maduro from office so he can establish a transitional government and hold new presidential elections.
FILE PHOTO: Venezuelan exiled veteran opposition figure and former mayor of Caracas Antonio Ledezma wears an Order Medal Of Cruzeiro Do Sul after receiving it form Brazil's Foreign Minister Aloysio Nunes Ferreira (not pictured), at the Itamaraty Palace in Brasilia, Brazil April 27, 2018. In the town of Urena, across from Cucuta, several hundred people dressed in white danced in the streets, waving flags and chanting profanities against top government officials.
Washington has said it will turn over control of those resources to Guaido once Maduro has been removed from power.
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Three million Venezuelans have fled the country since the economy collapsed in 2014.