The two-handled silver trophy was in use from 1896 until 1910.
The Football Association withdrew it after realising the design had no patent.
Auction house Bonhams said: “An astonishing piece of football history, the trophy charts the transformation of the game from one initially dominated by public school players to the popular mass-participation sport that it became and remains.”
As well as the names of the winners of the competition from 1896 to 1910, the privately-owned cup also carries the names of the 1872-1895 winners as the very first FA Cup was stolen and never recovered.
Managing director of Bonhams’ Knightsbridge Jon Baddeley said: “We are very proud to have been entrusted with the sale of this legendary cup. It embodies so much of the early history of our national game that it can, without exaggeration, be described as a national treasure.
“I anticipate a great deal of interest in the trophy.”
It will go under the hammer at Bonhams on Tuesday September 29.