All the polling stations for electing members to the National Constituent Assembly in Venezuela opened at 6:00 a.m. local time (1030 GMT) on Sunday, despite opposition-led protests against the move.
Protests have erupted across the country as the opposition decries the contest as a "power grab" by Maduro.
Despite four months of deadly protests and the threat of USA sanctions, Venezuela on Saturday found itself 24 hours away from a consolidation of government power that appeared certain to drag the OPEC nation deeper into a crisis that has entire neighborhoods battling police and paramilitaries while the poor root for scraps in piles of trash. Protesters say the election of a constitutional assembly will allow Maduro to eliminate democratic checks and balances and install an authoritarian single-party system. More than 110 people have been killed, many in clashes between the state and armed protesters.
On the eve of the vote, protesters blocked roads in the capital in defiance of a ban on demonstrations.
The Venezuelan leader has blamed the mounting unrest against him and his policies on the United States, working hand-in-hand with the Venezuelan opposition to wage an "economic war".
But Maduro has insisted that the "card that will win this game" is the election of the new assembly.
Only 23 percent of Venezuelans favor the new assembly plans, according to a June survey by polling firm Datanalisis.
Nearly 20 million Venezuelans are registered to vote for 545 members of the National Constituent Assembly.
"This is for elections, for the freeing of political prisoners, for change", said Opposition Congressman Freddy Guevera.
Several foreign airlines, including Air France, Delta, Avianca and Iberia have suspended flights to the country over worries about security.
The US, the European Union, the Organization of American States, as well as Argentina, Brazil, Colombia and Mexico oppose the election, warning it could decapitate Venezuela's democracy and lead to further unrest.
He said he wants the assembly to strip opposition legislators of their constitutional immunity from prosecution and indicated he is eager to prosecute many more members of the opposition parties that control a handful of state governments along with the National Assembly, providing one of the few remaining checks on the power of the socialist party that has ruled this OPEC nation for almost two decades.
Neighboring Colombia - a refuge for tens of thousands of Venezuelans fleeing the chaos at home - has said it would not recognize the results of Sunday's election in Venezuela.
The United States, who already impose sanctions against Venezuela, stepped up the pressure with President Trump promisingexternal link "strong and swift economic actions" if the assembly comes into effect.
The US has suggested further sanctions could follow. The oil industry is anxious they could target Venezuela's crude exports, 40 percent of which are bought by the United States.
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A police officer guarding the residence was injured in the attack, which comes ten days before a fiercely fought general election. The intruder was later forced to hide at a building under construction after reinforcement was called, added the IG.