In Venezuela on Tuesday (Wednesday AEDT), Guaido told a huge rally of supporters that humanitarian aid would enter the country on February 23, setting the stage for a showdown with President Nicolas Maduro who has refused to let supplies in.
Guaido's envoy to Brazil, Maria Teresa Belandria, said she had received assurances from Brazilian Foreign Minister Ernesto Araujo over the new aid centre.
A stockpile of USA aid - medicines, medical equipment and nutritional supplements - is in the Colombian border city of Cucuta.
"It's a political war of the United States empire", Maduro said in the interview, "of the interests of the extreme right that today is governing - of the Ku Klux Klan - that rules the White House, to take over Venezuela".
US President Donald Trump's administration has been pushing for the global community - including Israel - to back President Nicolas Maduro's ouster.
Jerusalem was reportedly hesitant to throw its backing behind Guaido amid concerns the Maduro regime would respond with measures that could imperil members of the Venezuelan Jewish community.
The protests, which were taking place on the country's Youth Day, had been called by self-declared acting president Juan Guaido, whose ability to mobilize the aid is seen as a key test in his power struggle with Maduro.
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Guaido said he was issuing a "direct order" to the armed forces to allow the aid in, though so far there are not clear signs the military will disobey Maduro.
The militia is a civilian force founded in 2008 to supplement the armed forces.
"Why do we protect the assets of Venezuela?"
German President Frank-Walter Steinmeier, who was visiting Colombia, said in the city of Cartagena that Venezuela was on the verge of bankruptcy and that the supply situation of the population was "dramatically bad". "We are motivated by work, production, and growth of our economy".
"There are many Venezuelans in Israel and many Jews in Venezuela", Guaido said. "I assume they are happy we are renewing ties with Israel".
But Guaido on Sunday reiterated that he would not negotiate with Maduro - as he believes Maduro would use such talks to buy himself time.
While keen on papal mediation, Maduro was less impressed last week when a group of European and Latin American ministers called for new presidential elections, accusing them of bias.
On Monday, Guaido posted a video on Twitter showing himself and his wife making phone calls urging people to join a volunteer force by registering on a website and calling on them to return to the streets in protest Tuesday.