Lagarde denies the charges of negligence, arguing she was acting "in the state's interest" in making the payment to Bernard Tapie, the former owner of sportswear giant Adidas and Olympique Marseille football club.
If found guilty, Lagarde could receive a one-year prison sentence and a 15,000 euro (USD 15,900) fine.
Whatever the outcome, the case risks damaging the image of 60-year-old Lagarde, a former corporate lawyer who progressed through the finance ministry to her current role as one of the world's most powerful women.
Lagarde, who was named to a second term in February this year, has received the full backing of the IMF over the case.
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She will be tried by the Court of Justice of the Republic, a tribunal that hears cases against ministers accused of wrongdoing in the discharge of their duties.
The accusations stem from Lagarde's handling of a dispute with Tapie, a former government minister who claimed a state bank defrauded him in its sale of Adidas.
Tapie owned the firm between 1990 and 1993 but lost control of it after he went bankrupt. He also owned Marseille when they won the 1993 European Cup, the forerunner of the Champions League, but they were later embroiled in a match-fixing scandal.
The decision was hugely costly, with Tapie initially walking away with a staggering 404 million euros (USD 427 million) in compensation in 2008. After a lengthy court battle, he has since been ordered to repay the money.
Investigators suspect the arbitration process was rigged in favour of Tapie, who had supported Sarkozy in his 2007 election campaign.
Lagarde, who served as finance minister until 2011, has always insisted she acted in France's best interests.
The prosecution says that through her actions, Lagarde "deprived the state of a chance to avoid this money being misused".
Others face fraud charges over the affair, including 73-year-old Tapie, his lawyer, one of the arbitrators, Lagarde's former chief of staff in the finance ministry and the current head of the telecom group Orange, Stephane Richard.