The singer will play the weekend event at Hyde Park on Sunday, July 3, a day headlined by reforming 90s Britpop group Pulp.
Wireless organisers said they were delighted to have signed Jones to the line-up.
In a statement they added: "With hit records spanning over 30 years, Grace is undoubtedly one of the most iconic and cutting edge artists of our time, with a sound and style firmly entrenched in pop culture history.
"Her distinct fusion of new wave, pop, reggae and R&B along with her striking, androgynous image has inspired legions of artists since her debut, whilst her enthralling live shows need to be seen to be believed."
On Friday July 1, Wireless hosts performances from The Black Eyed Peas, Plan B, Tinie Tempah, Bruno Mars, Example, Labrinth and David Guetta.
Saturday July 2 is headlined by The Chemical Brothers with support form Chase & Status, The Streets, Aphex Twin, Janelle Monae, Katy B, Battles, Devlin, Digitalism and The Whip.