His pledge followed comments by the US Ambassador to Colombia urging the Venezuelan military to allow the aid to enter the country.
He accused the Trump administration of trying to violate national sovereignty by co-ordinating the shipment of hundreds of tonnes of medicines, medical equipment and nutritional supplements.
"Civil society is no longer supporting Maduro, and bureaucrats are no longer doing what the government wants them to do", said a longtime opposition leader who served time in jail for helping his countrymen vote.
The 56-year-old said Venezuela's humanitarian crisis has been "fabricated by Washington" to justify an "intervention" in the South American country. His press conference in Caracas was twice interrupted by power cuts, which have become common in the capital.
A day after the USA aid convoy arrived in the border city of Cucuta, Maduro ridiculed the Americans for offering small amounts of assistance while maintaining sanctions that block some $10 billion of offshore assets and revenue.
The rapid and precipitous endorsement of Guaido's claim on the presidency of his country by the USA and several European and Latin American countries makes a mockery of recognised worldwide norms.
The Maduro government, responsible for an economic collapse that has reportedly forced some three million Venezuelans to flee the country, lashed out at the European Union nations, saying their move would damage relations with Caracas.
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"Inhibiting the entry of this aid could be seen as a crime against humanity".
"I'd be really disappointed if we didn't have a deal", Scott said.
Early Wednesday, a Venezuelan military boat carrying 100 tons (tonnes) of aid landed in Havana to help Cubans recovering from the wrath of a tornado.
With hawkish Trump White House officials like national security adviser John Bolton continuing to warn that USA military intervention in Venezuela remains "on the table", Maduro published an open letter to the American public urging opposition to "warmongering and war".
Guaido has called for the demonstrations to continue in the country in a bid to ramp up pressure on Maduro.
Guaido said 300,000 people could die if desperately-needed aid isn't brought in.
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However, she added that "China supports the efforts by the worldwide community to this end and hopes that all sides will continue to play a constructive role in the peaceful resolution of the Venezuela issue".
Venezuela's dire situation has fuelled a political crisis that has peaked over the last month with Guaido invoking a constitutional provision to declare himself the legitimate, interim president.
Opposition leader Juan Guaidó, the leader of the Venezuelan legislature, declared himself interim president and called for fair elections in response to the turmoil caused by Maduro's socialist government. "You're deaf... They've taken extremist positions".
He did welcome the Contact Group's proposal to send a mission to Venezuela, though.
So did the Lima Group countries (excluding Mexico), the Organization of American States, and a number of other countries.
The opposition-controlled legislature has been powerless since 2016 after it was stripped of its powers by the Supreme Court, made up of regime loyalists.
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