The Constituent Assembly has supreme powers over all branches of government as it takes on its principal task of rewriting the 1999 constitution. It was elected last weekend in balloting marred by violence and allegations of fraud.
Its 500-plus-members, who include Maduro's wife and son, are led by Delcy Rodriguez, Maduro's former foreign minister.
They took their seats in an ornate oval chamber under a golden dome in the 145-year-old Legislative Palace -- in the same building where the opposition-dominated National Assembly is located, albeit in a different room.
She rejected what she called "foreign interference" in the new assembly's creation.
The Constituent Assembly has discretion to dissolve the National Assembly. Such a move, however, would fuel criticism of it as a rubber-stamp body for Maduro, who critics say is building a "dictatorship."
The assembly's members were accompanied to the palace by Maduro and thousands of supporters carrying portraits of late president Hugo Chavez.
"The people today are going back to the assembly building and will never leave," said one supporter, 72-year-old Euclides Vivas.
The Vatican today had urged the assembly's session not be held, saying it contributed to "a climate of tension" in Venezuela.
Just hours ahead of the assembly's inaugural session, Venezuela's intelligence service unexpectedly transferred a high-profile opposition figure, Caracas mayor Antonio Ledezma, from jail back to house arrest, his family said.
Ledezma and another opposition figure, Leopoldo Lopez, had been taken from their homes to military prison on Tuesday, reversing earlier home detentions.
The Constituent Assembly marks a new stage in Venezuela's rule.
Maduro claims the revised charter will yank Venezuela out of its political and economic crisis, though he has not detailed how. Nor has he given an end date for the Constituent Assembly, which he said would operate for years.
The body is being challenged on several fronts.
Backing opposition allegations of fraud, Smartmatic, a British-based company involved in the vote technology behind the election last Sunday, said the official turnout figure had been tampered with and exaggerated by at least a million voters.
She said prosecutors had lodged court cases seeking to have the Constituent Assembly annulled, though few in Venezuela believed that would happen -- and the new assembly could also fire her as one of its first actions.
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