The man subsequently headed to a police station where he filed a complaint against Valerie Trierweiler over the incident yesterday, several sources said.
A source close to the affair who asked not to be identified said the row took place in Paris's southern 15th district.
The source said that according to the plaintiff's version of events, a cafe customer went up to Trierweiler and sarcastically asked how Hollande was doing. After an angry exchange, she allegedly slapped him.
But her stint as first lady ended brutally when a celebrity magazine published photos of the head of state cheating on her with actress Julie Gayet.
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News of the cafe slap was first released by RTL broadcaster, triggering a tweet from Trierweiler saying "A single word #stopboorishness", with no other comment.
A judicial source told AFP the complaint was filed on grounds of violent behaviour.
If the inquiry finds the alleged violence did not render him unfit to work for at least eight days, the complaint might lead to a fine by a police tribunal.