Traditional aid groups have shunned the effort as a political ploy, but Guaido is counting on the USA -backed initiative to persuade his country's military to recognize him, and to create an opening for desperately needed relief.
In an address to Miami's Venezuelan-American community Monday, President Donald Trump will say forces loyal to Caracas leader Nicolas Maduro have two choices - pursue democracy or lose everything they have.
Food supplies, hygiene kits and nutritional supplements have been stockpiled near the Venezuelan border in Cucuta, Colombia.
While Trump has refused to rule out a USA military intervention in Venezuela, Congressman Eliot Engel, the Democratic chairman of the House Foreign Affairs Committee, said during a congressional hearing last week that lawmakers would not support such a move.
Sometimes working under awnings or tents, doctors, nurses, dentists and paediatricians have attended to local residents who can receive donated medications.
An imploding economy has driven an estimated 2.3 million Venezuelans to migrate from the oil-rich country.
Yorger Maita, a helper from the aid group Rescate Venezuela, said that if foreign aid doesn't enter "other people will continue to die".
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The aid shipments have been meant in part to dramatize the hyperinflation and shortages of food and medicine that are gripping Venezuela.
Maduro says the aid is a "publicity show" and a pretext for a US-led invasion.
Trump supporters with a sign reading 'Pres.
The International Committee of the Red Cross (ICRC), in turn, cautioned USA officials against politicising humanitarian assistance and delivering aid without the consent of local authorities.
Three US military cargo planes delivered several dozen more tons (tonnes) of food assistance to Cucuta on Saturday.
Mr Maduro has dismissed the humanitarian assistance as "crumbs" and "rotten and contaminated food" while blaming shortages of food and medicine on United States sanctions.
Guaido said thousands of Venezuelans have volunteered to meet on February 23 to escort the aid through barricades constructed on an unused bridge that connects the two nations. Rodriguez did not announce the artists that are expected to perform, saying only that it would be massive.