A source close to the probe said the interrogation was pre-arranged with police and was part of the inquiry into the Relais & Châteaux chain, whose former chairman, Régis Bulot, is accused of involvement in fraud.
Bulot, 64, was taken into custody last November on charges of organised fraud and money laundering. He is suspected of embezzling €1.6 million ($2 million) between 2002 and 2008. He was released in June.
Villepin, 58 in 2011 allegedly made a phone call – bugged by police – on behalf of Bulot in which he bragged about putting pressure on the new management of Relais & Châteaux not to co-operate with a police probe.
The politician, who served as prime minister under president Jacques Chirac from May 2005 till May 2007, holidayed with his wife at a Relais & Châteaux resort on the French Caribbean island of Martinique in 2005.
Villepin, a suave diplomat best remembered for leading the charge against the Iraq war at the United Nations in 2003, has denied any knowledge of an embezzlement scheme.
He said in a statement on Tuesday after the hours-long interrogation that he had again told the investigators that "I am in no way implicated in this sad affair that is affecting one of my friends".
Prosecutor Brice Raymondeau-Castanet told AFP it was "probable" that a judge leading the probe would want to question Villepin at a later date.
Villepin was last year cleared of wrongdoing in an alleged smear campaign against ex-president Nicolas Sarkozy, a bitter political rival.
In September a lawyer widely reported to be close to Sarkozy also implicated Villepin in a scandal involving huge sums of cash allegedly handed over by African leaders to politicians.
Robert Bourgi said he had personally handed $20 million in cash from several presidents of France's former African colonies to Chirac and Villepin – a claim that both furiously denied.
In March this year Villepin announced he would form a new centre-right party and stand against Sarkozy in the presidential elections in April and May. But he failed to secure enough support for his candidacy to proceed.