The high court ruled that Rodriguez “assume and exercise, in an acting capacity, all the attributes, duties and powers inherent to the office of President…to guarantee administrative continuity and the comprehensive defense of the nation.”
The judges stopped short of declaring Maduro permanently absent from office, a ruling that requires holding elections within 30 days.
Maduro is the sole legitimate head of state, Rodriguez said following the US strikes on the country and the capture of the president of Venezuela.
“This country has only one president, and his name is Nicolas Maduro Moros,” she added in a speech broadcast on the Telesur television channel.
The United Nations Security Council will meet Monday to discuss the US operation to seize Maduro in Caracas, the Somali presidency of the Council told AFP on Saturday.
The emergency meeting, scheduled for 10:00 am (1500 GMT), was requested by Venezuela and relayed by Colombia, diplomatic sources announced.