The arrest of Diego Salazar comes amid a widening corruption probe into Venezuela's state-run oil industry that some see as an attempt by President Nicolas Maduro to consolidate power within his socialist party ahead of next year's presidential elections.
Many proteges of Ramirez have been detained, including former Oil Minister Eulogio del Pino and Nestor Martinez, ex- president of state oil company PDVSA.
Some observers see him as the ultimate target of the purge.
In a telephone interview broadcast on state-run television, Attorney General Tarek William Saab said Salazar is accused of money laundering and association to commit a crime.
Salazar and others would be linked to a corruption scheme in the bank in Andorra, a nation of 85,000 inhabitants between Spain and France, Saab said.
In 2015, Andorra intervened in the Banca Privada d'Andorra, or BPA, after the US Treasury Department accused it of laundering money from groups in China, Russia and Venezuela.
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