The legendary Plate 77 Penny Red was printed in 1864 and there are just nine examples of the stamp that still exist.
Three remain in private hands with the others in museums and the one currently being sold by Paul Fraser Collectibles is said to be in the finest condition.
With interest from around the world, the sale is expected to smash the previous record price set at £550k when the same example of the Plate 77 Penny Red sold in 2012.
The used stamp has a price of £650,000, a testament to its scarcity and legendary status.
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UK’s most expensive stamp on sale for £650k
The Victorians issued 21 billion Penny Reds, but just nine examples exist from printing plate 77.
The authorities only produced one sheet of 240 stamps from printing Plate 77 before they realised the plate was defective.
They destroyed the printing plate and the sheet, but nine stamps somehow escaped the incinerator.
Paul Fraser Collectibles’ CEO, Mike Hall, said: “This stamp is legendary among collectors because it shouldn’t exist.
“While most people know the Penny Black was the first stamp, it’s actually Plate 77 Penny Reds that send collectors into a frenzy.”
The Penny Red replaced the Penny Black in 1841 and the British postal authorities issued Penny Reds until 1879.
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A small “77” in the stamp’s right-hand scrollwork reveals its plate number
This example comes on part of its original envelope, accompanied by a four-penny stamp
Both have been stamped with a “15” cancellation, denoting its use in Highbury, London
The example was discovered by a Manchester stamp dealer in 1920.