Mr Guaidó said new collection points and routes into the country would allow volunteers to bring the aid in.
Mr Maduro told the BBC he would not allow aid in, claiming it was a means for the US to intervene in Venezuela.
Venezuelans are facing drastic food shortages amid an economic crisis.
"We have almost 300,000 Venezuelans who will die if the aid doesn't enter. There are almost two million at health risk," said Mr Guaidó at the rally on Tuesday.
Read MORE
