"This is a crime against humanity, men of the armed forces", Juan Guaido said.
He has vowed not to let in "fake" aid from the United States requested by opposition leader, which is being stockpiled at the border with Colombia.
Accusing those blocking aid of being "almost genocidal", he likewise warned that the military would be held responsible for the deaths of protesters - and reaffirmed his call for a mass march on Tuesday in memory of the estimated 40 people killed in disturbances since January 21.
Venezuela's self-proclaimed interim leader has told RT that the "corrupt regime" there is exclusively to blame for its dire humanitarian situation, and promised that democracy will be embraced, with free elections, once Maduro is gone.
The military exercises, which mark the 200th anniversary of the historic Battle of Angostura, will continue through Friday.
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Shipments of USA food, medicine, and humanitarian aid are on the Colombian side, with a tanker and two large trucks sitting in the middle of the bridge.
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.
And on Sunday, he said hundreds of volunteers had signed up over the weekend to help bring aid into Venezuela - with further shipments set to arrive in neighboring Brazil and on a Caribbean island.
The United States and dozens of other countries have recognized Guaido as the nation's legitimate head of state.
"Democracy is closer than ever before, the future is ours", he said.
It also "calls for the immediate start of a political process leading to free, fair and credible presidential elections, with global electoral observation, in line with Venezuela's constitution".
Somewhat dodging the question about when the "free and fair" elections - so craved by some foreign states and others who believe Nicholas Maduro "usurped" power amid the oppositions' boycott of last year's polls - might take place, Guaido refused to name any specific dates.