Three years in a similar role at Radio 1 followed before Williams transferred to Radio 5 Live, initially as an entertainment reporter. He formerly hosted the Weekend Breakfast show, first with Anna Foster, more recently with Eleanor Oldroyd on Saturdays and Caroline Barker on Sundays (ended 28 April 2013); he frequently presents in the absence of Richard Bacon and is sometimes a stand-in co-presenter of 5 Live's weekday breakfast programme. He also covered Colin Murray's absence, hosting FiveLive's comedy sports panel game, Fighting Talk. From January 2010 until April 2011, Williams hosted the Sunday-night Comedy Club on BBC Radio 7. From 13 May 2013 he switched to the late-night show - presenting the show from Mondays to Wednesdays, 10.30pm-1.00am, also taking Thursdays when BBC1's political discussion show Question Time is off-season; 5 Live runs a simulcast when this programme is shown, with further discussion hosted by John Pienaar and Stephen Nolan either side of its one-hour slot.
Williams used to feature on the schedule of commercial station XFM London, presenting from 10am till 2pm every Sunday.