He subsequently joined the Royal Shakespeare Company (RSC) in 1988 and appeared in The Constant Couple, Macbeth, The Tempest, The Man Who Came to Dinner (Gene Saks, Barbican) and King Lear as Edgar.

Elsewhere, he has also appeared as Laertes in Hamlet at the Bristol Old Vic (1991), Brian in William Gaminara's Back Up the Hearse and Let them Sniff the Flowers at the Hampstead Theatre (1992), Roland Maule in Noël Coward's Present Laughter at the Globe Theatre (1993), Biff in Death of a Salesman, alongside Ken Stott and Jude Law, at the West Yorkshire Playhouse in Leeds (1994), Tony in The Servant at the Birmingham Rep (1995).

He returned to the RSC for Simon Callow's stage adaptation of the film classic, Les enfants du paradis at the Barbican.

Between March and June 2011 he starred as Peter in Trevor Nunn's production of Flare Path at the Theatre Royal, Haymarket, alongside Sheridan Smith and Sienna Miller, as part of the playwright Terence Rattigan's centenary year celebrations.

[3] He appeared as part of the ensemble cast of the 2019 West and Middle Chinnock Christmas Show, as well as singing several sea shanties from Fisherman's Friends.

In 1991, Purefoy played James McCarthy, a young man accused of murdering his father, in "The Boscombe Valley Mystery," in Granada's The Case-Book of Sherlock Holmes.

He played Edward, the Black Prince in the film A Knight's Tale, Rawdon Crawley in Vanity Fair with Reese Witherspoon and Tom Bertram in the 1999 production of Mansfield Park.

He has played major roles in several television costume dramas, including Sharpe's Sword, The Tenant of Wildfell Hall, The Prince and the Pauper, The Mayor of Casterbridge, Blackbeard: Terror at Sea, Beau Brummell: This Charming Man, The Tide of Life, Camelot and Rome.

When his Wikipedia entry, which at that time referred to the rumours, was brought up in an interview with Alastair McKay, published in the January 2007 issue of Out magazine, Purefoy said, "I won't say whose it was, but there was a penis in the series that may have been slightly enhanced.

In February 2019, Hybrid (who provided the score to Interlude in Prague) released a short film to accompany their single "Hold Your Breath" from the album Light of the Fearless.