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Her performance led to a series of appearances on various British television shows, including Emmerdale. In 1992, Friel was added to the cast on the Channel 4 soap opera Brookside, where she gained greater exposure in the role of Beth Jordache. Though she only stayed on the programme for two years, Friel's lesbian kiss remains one of the most talked-about moments in British soap history. In 1995, Friel won the National Television Award for Most popular actress for her work on Brookside.

In 1996, Friel courted further controversy when she appeared in the television film The Tribe by Stephen Poliakoff, which included nudity and a much discussed menage-a-trois sex scene between characters played by Friel, Jonathan Rhys Meyers and Jeremy Northam.

In 1998, Friel appeared in the original Broadway run of Closer by Patrick Marber at the Music Box Theatre, She continued to establish herself as a film actress as Ewan McGregor's wife in "Rogue Trader" (1998), the biopic of Nick Leeson, whose financial dealings brought about the collapse of Barings Bank. She joined a stellar cast that included Kevin Kline, Michelle Pfeiffer, Christian Bale and Rupert Everett for another telling of "A Midsummer Night's Dream" (1999), playing Hermia, the love-torn daughter of an overly-controlling father (Bernard Hill) who wants her to marry another man (Bale). winning Drama Desk and Theatre World awards for her performance as Alice and in 2001, Friel made her West End stage debut in a fringe production of Lulu which also transferred to Broadway. Friel began making more of a name for herself in the United States, first by appearing in small independent films, followed by regular series work on television. She headlined the British-made “Mad Cows” (1999), playing a newly single mother who shoplifts and stages a prison break scheme with her best friend (Joanna Lumley) so she can find the couple who adopted her son. 

In “Sunset Strip” (2000), an affective and well-meaning film set in 1972 Los Angeles, Friel was a struggling fashion designer catering to the Strip’s myriad rock musicians. After playing the sultry nurse girlfriend of a barber (Barry McEvoy) who gets a job at an Irish insane asylum in “An Everlasting Piece” (2000), she traveled back to Napoleonic France to play a local woman in love with an army officer (Jean Marc Barr) in the swashbuckling romance, “St. Ives” (2001). Friel then gave a strong performance as the troubled and unpredictable Marina, lifelong best friend to the steady and bookish Holly, in “Me Without You” (2002).

Friel's film credits include playing Nick Leeson's wife Lisa in Rogue Trader opposite Ewan McGregor; David Leland's The Land Girls, which also starred Rachel Weisz and Catherine McCormack; All For Love with Richard E. Grant; A Midsummer Night's Dream with Michelle Pfeiffer and Christian Bale; Timeline, Me Without You opposite Michelle Williams; and Goal! and Goal! 2.

Friel's television work includes the short lived The Jury for the Fox Network and ITV1's Watermelon which was based on the novel by Marian Keyes. She currently plays Charlotte "Chuck" Charles in Pushing Daisies, a new TV series from the creator of Dead Like Me and Wonderfalls, for the 2007 season on the American network ABC. In November 2006 she was awarded an Honorary Doctorate by the University of Bolton for contributions to the performing arts. She finally scored a TV hit with “Pushing Daises,” an oddball, stylized tale of a man (Lee Pace) with the power to bring the dead back to life unless he touches them again; sending them back to a permanent death. Friel played his childhood sweetheart Chuck, whom he revives after she is murdered on a cruise ship, only to fall hopelessly in love and never be able to touch her again. In 2008, Friel earned her first Golden Globe nomination for her role in the highly-acclaimed series.

She has recently been seen as the face of Pantene Pro-V Ice shine in the UK, appearing in both television commercials and print advertising. Friel has also previously appeared in commercials for 3 Mobile and Virgin Atlantic. According to press reports, she was cast as Jenny in Gangs Of New York but was replaced by Cameron Diaz after one day on set when studio heads intervened (it was said that Diaz's aquaintance with Leonardo DiCaprio and high profile won her the role), turned down Rachel Weisz's role in The Mummy and narrowly missed out on a leading role in Fightclub to Helena Bonham Carter. Upcoming roles include Elizabeth Bathory in Bathory and Angel Makers opposite Helen Mirren.

In 2001, she began a relationship with actor David Thewlis, whom she met on a flight to Cannes. Their daughter, Gracie Ellen Mary Friel, was born on July 9, 2005 at London's Portland Hospital and weighed 7lb 4oz.