The arrests came a day after a vote to choose a much-condemned assembly that supersedes parliament.
Opposition leader Leopoldo Lopez (pictured) was arrested at his home, his wife has claimed
Lopez and Ledezma were both already under house arrest when they were picked up by the intelligence service.
The two men are Venezuela's most high profile opposition leaders. Both had called for a boycott of Sunday's vote for a so-called and all-powerful constituent assembly tasked with rewriting the constitution.
The children of Caracas Mayor Antonio Ledezma (pictured) - named Victor, Vanessa and Antonietta - also said on Twitter that the intelligence services had taken away their father
Both of their families said they held President Nicolas Maduro, the driving force behind the vote, responsible for the leaders' lives.
'They just took Leopoldo away. We do not know where he is or where they are taking him,' Lopez's wife Lilian Tintori said on Twitter.
The children of Ledezma - named Victor, Vanessa and Antonietta - also said on Twitter that the Sebin had taken away their father.
Opposition leaders and local media posted cell phone footage of Ledezma being taken away from his home forcibly.
Opposition lawmaker Freddy Guevara said the arrests were aimed at 'frightening us and demoralising us.'
Last night,Maduro brushed off new U.S. sanctions on him and condemnation at home and abroad of the newly chosen constitutional assembly, saying the vote has given him a popular mandate to radically overhaul Venezuela's political system.
Maduro said Monday evening he had no intention of deviating from his plans to rewrite the constitution and go after a string of enemies, from independent Venezuelan news channels to gunmen he claimed were sent by neighbouring Colombia to disrupt the vote as part of an international conspiracy led by the man he calls 'Emperor Donald Trump.'
'They don't intimidate me. The threats and sanctions of the empire don't intimidate me for a moment,' Maduro said on national television. 'I don't listen to orders from the empire, not now or ever ... Bring on more sanctions, Donald Trump.'
A few hours earlier, Washington added Maduro to a steadily growing list of high-ranking Venezuelan officials targeted by financial sanctions, escalating a tactic that has so far failed to alter his socialist government's behavior.
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