The document records the marriage of General August Hulin and Marie Jeanne-Louise Tiersonnier, and was one of the first signed by Napoleon after being proclaimed emperor of France in 1804, Palm Beach-based Lion Heart Autographs said.
The document also bears the signatures of six of Napoleon's marshals and other notables of the period.
Lion Heart Autographs plans to put the document on sale at an antiques fair February 10-16 at the Palm Beach convention center.
The dealer said it was only one of a handful known to exist in private hands.
Josephine de Beauharnais married Napoleon Bonaparte in 1796, but he divorced her in 1809 because she did not give him an heir.
The dealer will also be putting on sale a letter of Albert Einstein, US president Dwight Eisenhower's doodles on White House stationery and a letter from Charles Darwin to a friend who accompanied him on the voyage of the Beagle to the Galapagos Islands.
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