The drum and bass outfit headline with a DJ set at the event at Forest Farm in Essex on Saturday, June 30.
They are joined by Mercury Prize winner Ms Dynamite, Sub Focus, Mista Jam and Fabio.
Festival director Daniel May said: "We were blown away by the response to last year's event and can't wait to get 2012 under way.
"We've got an obsessive passion for what we do. It's about attention to detail: the artists, the sound, the visuals, the quality of the experience."
He added: "This is by enthusiasts for enthusiasts with some of the best names in electronic music. This year is going to be special."
Further acts over five specialist stages will be announced shortly.
A limited quantity of advance tickets are available now for £25, while standard tickets will go on sale for £40. VIP tickets are priced at £75.
Standard tickets can be reserved with a deposit of £20 and VIP passes for £37.50.
Last year at Bestival, Pendulum said that they had played their last show in the UK as a live band "for the foreseeable future".
> Ms Dynamite works with Emeli Sandé, Labrinth on new album
Watch the Ms Dynamite 'Neva Soft' music video below: