The Constituent Assembly unanimously adopted a decree authorising it to "take over functions to legislate on matters directly concerned with ensuring peace, security, sovereignty, the socio-economic and financial systems, state assets and upholding Venezuelans' rights."
The new assembly was ostensibly brought in to rewrite the constitution but has been handed sweeping powers to override all other branches of government.
"All the organs of public power are subordinate to the National Constituent Assembly," said the decree, read out at Friday's session.
The assembly -- led by Maduro's fiercely loyal former foreign minister, Delcy Rodriguez -- also includes his wife and son.
"We will not permit any more diverting of power" by the opposition, Rodriguez said Friday before the decree was read out.
"The constituent assembly is here to impose order."
International powers have accused Maduro of acting undemocratically.
Several Latin American countries have said they will not recognize the Constituent Assembly or its decisions.
The United States has imposed direct sanctions on Maduro.
Nearly 130 people have been killed this year in a wave of anti-government protests.
Opposition leaders in the elected National Assembly were summoned to attend Friday's session by the pro-Maduro constituent body but boycotted it.
They issued an open letter rejecting "the fraudulent National Constituent Assembly, its orders and all its acts.
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