The call to polls -- described as a "plebiscite" by the opposition, but "illegal" by the government -- is over Maduro's intention to have a citizens' body elected to redraft the country's basic law.
To detract from the opposition vote, his government was today holding a dry-run simulation of that election, which is to be held on July 30.
Several Latin American countries and the Catholic Church have criticized the move to draw up a new constitution, while the opposition has slammed it as bid by Maduro to concentrate dictatorial powers to stay in power.
"Liberty!" yelled some.
"We are turning out to show our discontent with the government," said 49-year-old Tibisay Mendez.
"We can't find medicines, every day there is less food in the country. And they (Maduro and his officials) only want to hold on to power. We are voting to get them out," she said.
The electoral struggle is being played out against a backdrop of pro- and anti-Maduro demonstrations -- which have left nearly 100 people dead since April 1 -- and a near- collapse of the oil-rich nation's economy.
Already early today in Caracas there were lines in parts of the city in front of makeshift polling stations.
Voters are being asked if they reject Maduro's plan to create a "Constituent Assembly" to redo the constitution, and if they approve of early elections.
Julio Borges, leader of the opposition-controlled parliament, said the vote "will denote a 'before and after' in this fight to win back democracy for Venezuela."
Both the opposition and the government have dug in on their respective courses, giving no heed to the other side. Attempts at dialogue have failed, and now each is talking to the public at cross-purposes.
Discontent has spiralled as the population suffers under a crushing economic crisis, with shortages of food and medicine and triple-digit inflation.
The opposition accuses Maduro of driving the country into bankruptcy, and of using the Constituent Assembly to entirely sideline the parliament.
The president, in turn, says the opposition is collaborating with the "imperialist" United States to undermine the economy, and to topple his government.
He has presented his 545-member Constituent Assembly, drawn from various sectors of society, as "the only path" to peace and economic recovery.
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