The opposition majority in the National Assembly legislature declared that Maduro effectively "abandoned his post" by failing to stem the "economic devastation" in the oil-rich country, according to the speaker of the legislature, Julio Borges.
However, the Supreme Court, which has consistently sided with Maduro, was expected to overrule the motion. It has stated that "the National Assembly is not qualified to remove the president."
The opposition blames Maduro for an "unprecedented economic crisis" that has prompted deadly riots and looting amid shortages of food and medicine.
Maduro has blamed the crisis on a US-backed conspiracy against his socialist policies inherited from his late predecessor, Hugo Chavez.
The opposition wants to hold early elections, saying the situation is too serious to wait until Maduro ends his term in 2019.
"An electoral end to Venezuela's crisis is needed. So that the people can express themselves through a vote," Borges said.
The lawmakers' declaration accuses Maduro of trampling citizens' rights and "breaking with the constitutional order."
But Maduro has easily swatted down the opposition's other maneuvers against him so far.
His grip on the courts, electoral council and military has allowed him to stymie a series of opposition strategies: a recall referendum, legislative onslaught and street protests.
The Supreme Court five months ago declared null all acts passed by the opposition-dominated parliament. It maintains that Maduro is exercising his constitutional prerogatives.
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