Attorney General Tarek William Saab told journalists that the former minister Eulogio del Pino and ex-PDVSA boss Nelson Martinez were picked up in a dawn operation by the country's Military Counterintelligence Unit.
Both former officials were arrested at their homes, four days after they were axed from their jobs by President Nicolas Maduro.
State television images showed black-clad security forces, their faces covered and armed with rifles, knocking on the door of Del Pino's apartment.
Saab said Del Pino was accused of "intentionally altering oil production figures" and said the arrests were part of an operation "to dismantle the cartel that has been hitting the oil industry."
He said he had ordered the arrests of 16 people as part of the operation, some of whom were "outside the country," adding: "We hope they will be delivered to Venezuelan justice."
Martinez was charged in connection with alleged fraud at PDVSA's US-based affiliate Citgo.
Del Pino and Martinez are the highest-ranking officials arrested as part of an anti-corruption purge at PDVSA, the state oil giant which accounts for almost all the country's income.
"This sabotage plan is aimed at achieving a repeat of 2002-03 when there was an attempted coup" against former president Hugo Chavez, Quevedo said.
Last week, the Venezuelan authorities arrested six Citgo executives for allegedly signing contracts to refinance USD 4 billion in debt without government approval. The government alleges that a USD 50 million bribe was paid as part of that deal.
Today's arrests come amid what analysts say is an aggressive push by Maduro to consolidate power over the country's key institutions and increasingly scarce resources ahead of next year's election.
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