Dominique de Villepin has been placed under police custody for the interrogation, which was pre-arranged, a source told AFP news agency.
He is being asked about an alleged intervention in the Relais & Chateaux fraud inquiry, Le Monde reports.
The former prime minister previously denied involvement in the case.
A close friend of Dominique de Villepin, Regis Bulot, is accused of embezzling 1.6 million euros ($2 million) between 2002 and 2008.
Regis Bulot, who formerly headed the Relais & Chateaux luxury small hotel association, has been in custody since November. He denies the charges against him.
The former prime minister was brought into the case when police secretly recorded a telephone conversation between the two men in early 2010.
In the bugged phone call, it is alleged that Dominique de Villepin claimed to have put pressure on the new management of Relais & Chateaux not to co-operate with the police investigation.
Dominique de Villepin was cleared a year ago of wrongdoing in an alleged smear campaign against former President Nicolas Sarkozy.
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