Maduro, in a televised address from the presidential palace, said Ledezma had been taken into custody on order of the attorney general.
Venezuelan opposition leaders said earlier that Ledezma had been arrested after security police searched his office.
The arrest came a day after the anniversary of the arrest last year of Leopoldo Lopez, another opposition leader and former mayor of Caracas' Chacao borough. Ledezma, 59, is overall mayor of metropolitan Caracas, although Maduro’s late predecessor,
Ledezma's wife, Mitzy, first sent word of her husband's arrest over social media. She told the Venezuelan Internet channel Vivo Play that she was present when police took him away and that arresting officers struck the mayor and her.
"They arrested him savagely. They hit him," the mayor's wife said.
Chacao borough council member Alfredo Jimeno wrote on his Twitter account that Ledezma had been arrested. Police reportedly fired a weapon into the air after staffers tried to impede the arrest.
Lopez has been held for a year in a military prison on charges of inciting violence during last year's student demonstrations, which swept many cities, leaving 43 dead. He insisted that he advocated peaceful protests and many human rights groups, including one under the United Nations umbrella, have called on Maduro to release him.
Lopez's wife, Lilian Tintori, said that since Feb. 12 Lopez has been kept in solitary confinement. On that day, close Maduro ally and National Assembly President Diosdado Cabello accused Ledezma and opposition Assembly member Julio Borges of plotting to overthrow the government.
Cabello also announced then that several military officers had been arrested for allegedly planning a coup against the Chavista government.
In March, after bloody protests swept the country, Mayors Daniel Ceballos of San Cristóbal and Enzo Scarano of San Diego were arrested, accused of not heeding government orders to squelch protests. Scarano is receiving medical treatment outside Venezuela, and Ceballos remains in jail. As many as 60 students arrested during last year's unrest are thought to be still in jail.
Jose Miguel Vivanco, director of