Pickering also performed in Bugsy Malone; as the Artful Dodger in Oliver Twist; and in The Long and the Short and the Tall on various London stages; before starring opposite Helen Mirren and Julie Walters in Calendar Girls in 2003. He then returned to the stage as Joseph Merrick in The Elephant Man. The production did not use prosthetics, to encourage the audience to see Merrick's struggle and emotions.

Pickering's most significant television role was in Peter Kay's 2008 talent show parody Britain's Got the Pop Factor..., in which he played R Wayne, a role that involved singing and dancing.

Additionally, Pickering plays Montparnasse in Tom Hooper's 2012 reimagining of the celebrated musical Les Misérables.

In 2014, Pickering portrayed Enoch "Nucky" Thompson in his younger years, in the fifth and final season of the HBO television series Boardwalk Empire.

From December 2015 through January 2016, Pickering played Abanazar in Aladdin at the Milton Keynes Theatre. In April and May 2016, he was in the European debut of the rock musical The Toxic Avenger at the Southwark Playhouse, London.

He also had a bit part as a hapless pizza delivery man in 6th episode of the third series of the BBC comedy Josh which aired on November 6th 2017.