The chiffon print frock, created by Thai-based designer Disaya, could fetch between £10,000 and £20,000 when it is auctioned off later this month.
Profits from the sale will go to the Amy Winehouse Foundation – the charity set up by the late singer’s parents in a bid to help young, vulnerable people.
The dress will be sold at the Passion For Fashion auction at Kerry Taylor Auctions, in London, on 29 November.
Disaya lent the dress to the then relatively unknown Winehouse in 2006, when the singer’s stylist Louise Winwood was searching for clothes for her to wear for the cover of second album Back To Black.
After the photo-shoot, the frock was returned to the designer and stored away in her archive. The album, meanwhile, went on to sell more than 3.2 million copies.
Following Winehouse’s death in July, Disaya decided the outfit should be displayed and sold to raise money for the Amy Winehouse Foundation.
Speaking about the dress, auctioneer Kerry Taylor said: “In my opinion, what makes this particular dress so special, is that it is an emblematic reminder of the magic voice and sublime talent of Amy Winehouse – a sound that resonates with an entire generation and always will.
“I am pleased to help raise funds for her charity and encourage fans, the music industry and museums the world over to bid with us on November 29th.”
Also going under the hammer at the Passion For Fashion auction are the dress worn by Audrey Hepburn to collect her Oscar for Roman Holiday in 1954, and two gowns worn by Elizabeth Taylor.