The black felted beaver fur "bicorne" hat is valued at between 300,000 and 400,000 euros (USD 375,000-USD 500,000), but experts think it could fetch four or five times that amount.
During his reign as French emperor -- from 1804-1814 and again in 1815 -- Napoleon Bonaparte is said to have worn around 120 of the hats.
Made by French hatmakers Poupard, Napoleon wore them sideways -- rather than with points at the front and back -- so he could be easily spotted on the battlefield.
The hat is the most emblematic item of the two-day sale at Fontainebleau on Saturday and Sunday.
Other items due to be sold by French auctioneers Osenat, Binoche and Giquello include a pair of Napoleon's stockings, a scarf and a shirt.
All come from a collection of around 1,000 pieces of Napoleon memorabilia that belonged to Prince Louis II of Monaco (1870-1949), the great-grandfather of current monarch Prince Albert.
The hat was acquired by Joseph Giraud, a vet in Napoleon's household, and remained in his family until 1926 when it was sold to Prince Louis' collection.
The Grimaldi family are selling a number of pieces having decided to pursue new museum projects.
"It's a very well-known collection, the provenance of the pieces is incontestable," Thierry Lentz, director of the Napoleon Foundation, told AFP.
The bicorne, meaning two horizonal points, was a variation on the tricorne -- or three-pointed hat -- which was popular in the 17th century and favoured by American colonists around the time of the American revolution.
And a fine-weave cotton shirt he also wore in exile could fetch 40,000 euros, the auctioneers believe.
Two hundred years after his reign, Napoleon remains a deeply popular historical figure. The main French association in his memory currently has around 4,000 members.
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