Duophonic's first release was Stereolab's debut EP Super 45 (1991), limited to 880 copies; of these, forty copies had handmade covers that were produced by Martin Pike in his father's garage.

Bands that have released records on Duophonic include Broadcast, the High Llamas, Labradford, Tortoise, Pram, Yo La Tengo, the Notwist, and Apparat Organ Quartet.

Daft Punk, one of the most successful electronic bands of the 1990s, released their first songs under the name Darlin' on the 1993 Duophonic compilation Shimmies in Super 8.

Duophonic's most successful release is Stereolab's Emperor Tomato Ketchup (1996), which was licensed to Elektra Records outside the UK and has sold over 60,000 copies worldwide.

Although founded in 1991, the label did not become a limited company until 25 August 1993, when Pike relocated from Horsham, West Sussex, to East Dulwich in the London Borough of Southwark.