The shirt was worn by Wolves outside right Thomas 'Tancy' Lea in the FA Cup final against Spurs at Stamford Bridge on April 23,1921.
It is deemed particularly valuable because it rained so heavily in south London that day that by the end of the first half the Wolves players were completely drenched and had to change into dry shirts at half time.
Experts know the shirt coming up for sale at Graham Budd Auctions in London on May 18 was worn by Tancy Lea in the first half as it features an embroidered silk badge bearing the Coat of Arms of Wolverhampton,with the motto: Out Of Darkness Cometh Light.
The shirts worn by the Wolves team in the second half of the 1921 FA Cup final did not feature such badges.
Lea was born in Oswestry in 1893 and played for Oswestry Town before moving to Wolves, where he played from 1913 to 1921.
Auctioneer Graham Budd, who has been involved in sports memorabilia auctions for 17 years, said the shirt is extremely rare and he has never seen another Wolves shirt from the first half of the 1921 FA Cup final.
The 1921 FA Cup final was the fifth of Wolves' eight FA Cup finals.They won the FA Cup in 1893, 1908, 1949 and 1960, but were runners up in 1889, 1896, 1921 and 1939.
They reached the 1921 final by beating Stoke City, Derby County, Fulham, Everton and Cardiff City in earlier rounds, only to lose 1-0 in the final against Spurs, whose winning goal was scored by Jimmy Dimmock.
King George V was amongst the 72,805 who watched the match on April 23 and afterwards presented the cup to Spurs captain Arthur Grimsdell.
The match took place at Chelsea's ground, Stamford Bridge, as it would be another two years before the first FA Cup final was staged at the gleaming new £800,000 Wembley Stadium in 1923.
The Wolves 1921 FA Cup final all English team,managed by Jack Addenbrooke, included Noel George, Maurice Woodward, George Marshall, Val Gregory, Joe Hodnett, Alf Riley, Tancy Lea, Frank Burrill, George Edmonds, Arthur Potts and Sammy Brooks.
The 1921 victory for Tottenham Hotspur represented the second example in what would become an odd 20th century 'tradition' for the club – that of winning years ending in the number one. They won in 1901, 1921, 1961, 1981 and 1991.