PDVSA's move comes after the United States imposed tough, new financial sanctions on January 28 aimed at blocking Venezuela's President Nicolas Maduro's access to the country's oil revenue. Maduro still retains the crucial backing of the country's military top brass, who control the repressive apparatus created to protect the regime's authority and crush political dissidents by force.
Armed military forces have continued to guard a blocked bridge between Venezuela and Colombia, cutting humanitarian aid off from the country.
Guaido's envoy to Brazil, Maria Teresa Belandria, said she had received assurances from Brazilian Foreign Minister Ernesto Araujo over the new aid centre.
The military exercises will last until February 15 and are set to become the most major and important drills that Caracas has held over its 200 year-old history, according to Maduro.
Guaido countered that the regime was refusing to acknowledge a "crisis that they themselves generated", while Venezuelans were working to deal with the humanitarian emergency.
The declaration came on the heels on a statement from U.S. Treasury Secretary Steven Mnuchin that all proceeds from sales of Venezuelan crude to U.S. refiners would be withheld unless PDVSA recognized Guaido as the legitimate leader of the country, which the company has not done so far.
But Guaido on Sunday reiterated that he would not negotiate with Maduro - as he believes Maduro would use such talks to buy himself time.
Over recent weeks, millions of Venezuelans have rallied around their president, Juan Guaidó, recognized by the USA and dozens of democracies around the world as the nation's legitimate leader following his constitutionally approved inauguration on January 23.