Military officers still loyal to Mr Maduro have used a truck tanker and huge shipping container to block access to the Tienditas bridge which links Colombia and Venezuela at the key border town of Cucuta.
A United States official said the aid will be kept at the main Colombian-Venezuelan border crossing at Cucuta with more supplies being prepared in Brazil and in the Caribbean.
Venezuela's state oil firm PDVSA is looking to sell more of its oil to customers in Europe and Asia as the US sanctions are cutting off USA buyers of its crude, a senior Venezuelan oil official loyal to Nicolas Maduro told Russian news outlet Sputnik in an interview published on Wednesday.
Police who provide security on the Colombian side of the bridge told Reuters there has been a huge number of Venezuelans asking when and where the aid will be delivered. Immigration authorities say the Venezuelan National Guard built the roadblock a day earlier.
Last week, the U.S. Russia, Belarus, Bolivia, Iran, China, Cuba, Nicaragua, El Salvador and Turkey stood up for Maduro's support.
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Pompeo on Tuesday thanked European countries that recognized self-declared Juan Guaido as interim president of Venezuela with a Twitter post and shared an animated graphic showing the nations which recognized Guaido.
Their meeting comes amid massive protests in Venezuela aimed at pressing Maduro, the country's socialist leader, to vacate the presidency.
Peering through cracks in a sheet metal fence to an area where US humanitarian aid is due to be stockpiled in Cucuta, Venezuelan Yesica Leonett pleaded for information on how her four children can benefit from the donations.
Venezuela's National Assembly, headed by self-proclaimed acting president Guaido, was to discuss the process of gathering badly-needed food and medicines in neighbouring countries before bringing it in.
He said: "I anticipate having perhaps a dozen locations all around Venezuela where such aid will be staged". "We can not buy drugs in Venezuela, you die before you get them". "We are not beggars".
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Canada and its Latin American allies in the Lima Group, along with the United States, have been pushing for Maduro's departure.
He thanked each European Union country in turn on Twitter "for supporting all Venezuelans in this struggle we undertake to rescue our nation's democracy, freedom and justice".
But a defiant Maduro maintains control of the military and calls the Guaido-led opposition a puppet of the United States, which he says is seeking to colonise Venezuela and exploit its vast oil resources.
The U.S. last week backed Venezuela's opposition leader, Juan Guaidó, along with Canada, Argentina, Brazil, Chile, Colombia, Costa Rica, Ecuador, Guatemala, Honduras, Panama, Paraguay, and Peru.
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