The embroidered blue velvet cap from the match against Czechoslovakia in 1963 is up for sale at Mullock's Auctions in Church Stretton.
Moore received the cap at the age of 22, making him England's youngest ever captain, and it was put up for sale by a member of his family.
Ben Jones, consultant at Mullock's, said: "Most of his collection sold in 2009 but this was kept back for one reason or another by the family.
"What makes it really important is that its his first cap as the England captain. He got 108 caps in total and is still to this day a massive name in football history. The fact that it was his first makes it even more special.
Mr Jones added: "I hope we get a lot of interest. Sometimes items this big can scare people off but sometimes things like this we will get interest from all over the globe - that's the thing with auctions, you can never be sure what is going to happen.
"I would like to see it kept in England but we will have to see what happens on the day."
But the sale of the cap has been met with some controversy.
England fans say that the cap is a 'national treasure', should be in a football museum and have called on the Football Association to step in and buy it.
Two other caps to be sold are valued at £6,000 each and were for Moore’s appearances against Portugal in 1964 and Yugoslavia in 1972.
He is one of the most iconic names in Football History and regarded as one of the greatest defenders of all time.
The sale takes place at the auction house on November 21.