President Maduro has announced a 60-day emergency, giving soldiers and police wider powers to deal with the country’s spiralling economic crisis.
Mr Capriles said the decree gave the president unconstitutional powers.
He called on Venezuelans to ignore it and take to the streets on Wednesday.
“We, Venezuelans, will not accept this decree. This is Maduro putting himself above the constitution,” Mr Capriles told journalists.
“To impose this, he’d better start preparing to deploy the war tanks and military jets,” he added.
“And I tell the armed forces: The hour of truth is coming, to decide whether you are with the constitution or with Maduro,” he said.
Mr Capriles said the opposition was not calling for a military coup, but instead seeking a legal and constitutional way of ousting Mr Maduro through a recall referendum.
The state of emergency is in place for 60 days and can be renewed for another 60.
The decree was rejected by the opposition-held National Assembly late on Tuesday, but Mr Maduro had indicated that he would not abide by their decision.
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