Commercial planes had been used for earlier aid shipments.
The US Air Force has begun flying tons of aid to a Colombian town on the Venezuelan border as part of an effort meant to undermine socialist President Nicolás Maduro.
Later Friday, Maduro asked the military to prepare for a "special deployment" to reinforce the border with Colombia - and make it "impregnable".
USA national security adviser John Bolton made the announcement on the aid pledged to Venezuela following an Organization of American States conference on assisting the country.
The European Union must recognize Venezuelan congress leader Juan Guaido as the president of the South American country, U.S. Vice President Mike Pence said on Saturday, pressing not just individual European governments but the bloc as a whole.
Humanitarian aid has become a key issue in the power struggle between Maduro and Guaido.
Speaking at a rally of volunteers in Caracas, Guaido said the "end of poverty will come, the humanitarian emergency will cease", urging that the aid be let in and "humanitarian corridors open".
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Venezuela is in the throes of an economic crisis, amid hyperinflation and shortages of food and medicine.
"Today, 25 countries, united at the OAS-hosted Conference on Humanitarian Assistance in Support of Venezuela pledged $100 million in humanitarian assistance", Bolton tweeted.
Three Air Force C-17 cargo planes from Homestead Air Reserve Base in Florida carried food and other aid to Cucuta.
He went on to say that Venezuela received 933 tons of medicines and medical supplies from Russia, China and Cuba on Thursday.
He said: "While we acknowledge significant risks to this baseline, our baseline is that regime pragmatists will turn on Mr Maduro and form a transition government with Mr Guaidó".
Maduro says the 35-year-old National Assembly speaker is a puppet to the USA, which is trying to secure access to Venezuela's gold and vast oil reserves - the largest in the world.
President Donald Trump this week repeated his warning to Maduro that "all options" are on the table, including military.
On Friday, Washington added to the political pressure on Maduro by sanctioning the head of Venezuela's oil company as well as top intelligence officials.
Some 30 European countries have already recognized the former industrial engineer as Venezuela's leader, but holdouts include Italy and Greece.