Four motorbikes and seven patrol cars belonging to the SEBIN intelligence service were seen outside the Caracas home of the ex-attorney general, Luisa Ortega, AFP journalists observed.
"At this moment SEBIN is searching my home as revenge by this government for my fight against totalitarianism," Ortega wrote on Twitter.
She did not say where she and her husband were.
Ortega was sacked two weeks ago as the first act of a new supreme assembly loyal to Maduro that has set about quashing dissent and hemming in the opposition, which controls the rival legislature.
Earlier Wednesday, her successor, Tarek William Saab, said he had asked officials to go after Ortega's husband, German Ferrer, a former loyalist lawmaker who has split from the ruling Socialist Party.
The charges have "nothing to do with" the political leanings of Ferrer or Ortega, Saab said.
He accused Ferrer of being part of a network trying to extort money from businessmen linked to Venezuela's all-important oil sector, promising them protection from prosecution on corruption allegations in exchange for money.
A decision on whether to grant an arrest warrant against Ferrer -- who has parliamentary immunity -- rests with Venezuela's supreme court, which up to now has systematically sided with Maduro.
Ortega in recent weeks accused Maduro of "dictatorial ambitions."
She rebelled against his administration in April when the supreme court tried -- before reversing course -- to assume the powers of the legislative National Assembly.
Her criticism sharpened when Maduro then set about creating the rival Constituent Assembly, which is packed with his supporters.
Most major countries in the Americas, including the US, Canada, Brazil, Argentina, Mexico and Chile have dismissed the Constituent Assembly as illegitimate and a tool to undermine Venezuelan democracy.
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