De Villepin said: "Nothing justifies this decision to go to trial. Throughout the judicial investigation, the reality of the facts and of the law has been twisted in favour of a single plaintiff who is at the same time president of the republic."
Also ordered to stand trial were: Jean-Louis Gergorin, a former senior executive of EADS, the European aircraft maker; Imad Lahoud, a computer specialist; Denis Robert, a journalist; and Florian Bourges, a former consultant.
The scandal first emerged in 2004, when a magistrate working on a corruption case received information about secret accounts at Clearstream, a Luxembourg securities clearing house, apparently held by Sarkozy and dozens of other senior figures.
The accounts proved to be fake and the investigation soon switched to uncovering who was behind the affair.
Speculation focused on de Villepin, who had ordered intelligence officials to conduct a secret investigation of the purported accounts, documents from which were then passed to the magistrate.
The informant was subsequently revealed to be Gergorin, who had close ties to the intelligence services as well as serving as an EADS executive.
Sarkozy became a plaintiff in the Clearstream case in 2006.
The trial, which is likely to be a drawn out affair, is expected to begin in 2010 and will re-open one of the biggest scandals of the era of Jacques Chirac, the former French president.
De Villepin, a career diplomat best known for his denunciation of the US-led invasion of Iraq in 2003, was one of Chirac's closest allies, first as chief of staff and then as foreign and interior minister before becoming prime minister in 2005.
He and Sarkozy, who once served as his interior minister, were rivals to succeed Chirac in the Elysee Palace.