Police broke into Caracas mayor Antonio Ledezma’s office and carted off the long-time critic of Venezuela’s socialist government.
The arrest added to tensions on the anniversary of the outbreak of protests that paralysed the nation a year ago.
President Nicolas Maduro took to television and radio to say that Mr Ledezma, one of the most vocal opposition leaders, would be punished for trying to sow unrest in Venezuela, which is struggling with severe economic problems.
Emotions were already running high before dozens of men in flak jackets and camouflage uniforms smashed down the door of Mr Ledezma’s office and forcibly carried him out of the building.
As news of the incursion spread across the capital, people spontaneously banged pots from their windows in protest while drivers tapped rhythms on their car horns in rush hour traffic.
As night fell, a few dozen people vented their anger in front of the headquarters of the intelligence service police, where Mr Ledezma was thought to be.
“He’ll be held accountable for all his crimes,” Mr Maduro said in a speech that TV and radio stations across the country were required to carry.
Last week, Mr Maduro named Mr Ledezma among government critics and Western powers he accused of plotting a coup to bring down the government.
It was one of more than a dozen such denunciations Mr Maduro has made since taking power in 2013.
Mr Ledezma mocked the accusation in multiple interviews, saying the real destabilising force in Venezuela was the government’s corruption.
Tensions have been running high in Venezuela with the one-year anniversary of the start of weeks of anti-government street protests that choked the country with tear gas and smoke from flaming barricades and resulted in more than 40 deaths.