Manuel Rosales, who said he wanted to take part in December’s parliamentary elections, was detained shortly after landing in the city of Maracaibo.
The politician ran against the late President Hugo Chavez in 2006.
Manuel Rosales, 62, fled to Peru in 2009 amid corruption allegations, which he says are politically motivated.
He was arrested on October 15 as he arrived at Maracaibo from the Dutch Caribbean island of Aruba. He is expected to appear in court in Caracas shortly.
Manuel Rosales is charged with corruption during his term as governor of Zulia state between 2000 and 2008.
He had announced on October 9 that he was planning to return to Venezuela.
Shortly before departing from Aruba Manuel Rosales posted a picture of him boarding.
He tweeted: “With God and the Virgin Mary, preparing to go to Venezuela to meet my people again.”
Venezuela’s Attorney General Luisa Ortega Diaz had warned that there was an arrest warrant against him.
Venezuelans go to the polls on December 6 for the first parliamentary elections since President Nicolas Maduro was elected in 2013.
Venezuela is facing a serious economic crisis, which the opposition blames on failed socialist policies of Hugo Chavez and his successor, Nicolas Maduro.
The government says Venezuela has been hit by a sharp drop in international oil prices, but it also accuses powerful groups of boycotting the economy to destabilize Nicolas Maduro.
Several other opposition leaders have also been detained since last year.
Last month, prominent opposition leader Leopoldo Lopez was found guilty of inciting violence during protests in 2014 in which 43 people – from both sides of the political divide – were killed.
Leopoldo Lopez was sentenced to 13 years and nine months in prison.
The US government and the UN have called for the release of the opposition politicians.
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