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Aimee Duffy's parents divorced when she was 10, and she moved to Pembrokeshire with her mother and sisters. She dropped her first name at the age of 19, calling herself Duffy professionally and personally.

Duffy's early interest in singing was apparently inspired by a videotape of the 1960s television rock show Ready Steady Go!. Duffy started singing at age 6 and at that age carried around a notebook in which she scribbled lyrics. She was booted from her school choir because her voice was "too big" and she "didn't fit in."

After finishing her GCSEs in Pembrokeshire, Duffy returned to Nefyn when she was 15, and started singing in various local bands. Following a 1-year long music project in Switzerland with co-writer and producer Soren Mounir under the name of Soulego, Duffy returned to Wales in 2003 and was invited to appear on Wawffactor, a Welsh television show on S4C. She was expected to win, but came second to winner Lisa Pedrig.

At age 18, thinking that her dreams of becoming a world famous pop star were not going to come true, she "became almost a quite withdrawn singer." After a re-evaluation she decided to just make music for no other purposes than her own fulfillment.

Duffy was elected president of the Students' union at Coleg Meirion-Dwyfor in Pwllheli, North Wales before transferring to the University of Chester in England. Advised by a lecturer to "Go on the dole, love, and become a singer," she left and worked for an optician, while building up a following at Alexander's, a local jazz and blues club, performing with guitarist David Burton from the band The Invisible Wires. She recorded a three-song Welsh EP in 2004 and also appeared on two tracks on the album See You in the Morning by Mint Royale while working as a waitress and in a fishery.

Contracted to A&M Records during 2007, on 23 November 2007, together with another rising star, Adele Duffy was the most prominent of the so-called "new Amys" (a reference to singer Amy Winehouse. Under the sub-title, "The New Amys", Adam Thompson wrote in The Times on 30 December 2007 that "Duffy, Gabriella Cilmiand Adelelead the charge to be the next Winehouse."

Her debut album, entitled Rockferry, was released on Polydor Records on 3 March 2008. According to Duffy "The album took nearly four years to make. We had to hire cheap, tiny studios and sometimes there would be three-week periods between writing and recording." The producer for the album was Bernard Butler who was not initially paid. After releasing a debut limited edition single, "Rockferry" in November 2007, Duffy then released a follow-up single, "Mercy", which went straight to number one on download sales on 17 February 2008. Duffy is the first Welsh female to achieve a number one pop single in the past 25 years, and the only female from the Llŷn Peninsula to ever top the UK music singles charts. "Mercy" spent a second week at number one on 24 February 2008, and set its full physical release on 25 February 2008.

In North America Duffy is seen as the latest in a recent wave of British singers or "British invaders" consisting of females with a unique take on writing and performing songs. This has been compared to the original "wave" led by The Beatles and The Rolling Stones.

Duffy won the 2008 Song of the Year MOJO Award for "Mercy". She was also nominated for Album of the Year and Breakthrough Act. The three nominations were the largest amount of nominations for any one act.