Bassey is the first solo female music artist to be honoured with a dedicated stamp issue.
Eight stamps are part of the main set and they show Dame Shirley performing throughout her career.
A further four stamps which are presented in a miniature sheet capture her during recording sessions and rehearsals.
Dame Shirley Bassey’s career to be celebrated with Royal Mail stamp set
The stamps include Dame Shirley singing at the Pigalle nightclub in 1965, in Bournemouth in 1974, at the BBC Electric Proms in 2009, singing World In Union (with Bryn Terfel) during the Opening Ceremony of the Rugby World Cup in 1999, and performing during the Oscars at the Dolby Theatre, Hollywood in 2013.
Dame Shirley said: “I am absolutely thrilled and would never have dreamed that one day my face would be on a stamp – that one day a letter might arrive and there I am, with a postmark next to me!
“It’s an absolute honour to be the first solo female artist to receive a collection from Royal Mail. The stamps are wonderful, and I hope my fans and collectors love them as much as I do.”
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David Gold, Royal Mail’s director of external affairs and policy, said: “For seven decades Dame Shirley Bassey has captivated fans across the world with her distinctive and powerful voice.
“This stamp issue is a fitting celebration of one of the UK’s most revered and longest serving musical icons.”