Richard Hawley, Doves, Magazine and Florence & The Machine also appear
Williams will take to the stage at Camden‘s Roundhouse venue on October 20 accompanied by a string and horn section, as well as his band.
He joins the likes of Dizzee Rascal, Doves and Florence And The Machine who are also playing the festival held October 20-24.
Meanwhile Shirley Bassey will premiere her new album ‘The Performance’ at her show on October 23. The album features tracks written by Manic Street Preachers, Take That‘s Gary Barlow and Kaiser Chiefs.
“What I’m most looking forward to at the BBC Electric Proms is performing songs from my new album ‘The Performance’ for the first time – it really will be a special moment for me,” she said.
Richard Hawley will also play on the same night.
Tickets for the latest BBC Proms shows go on sale at 8am (BST) tomorrow (September 23).
See BBC.co.uk/electricproms for more information.