Elbow, The Black Keys, Robert Plant, Blondie, Massive Attack, M.I.A and Skrillex will also perform at the massive outdoor festival over the weekend of June 27 to 29.
Arcade Fire will headline on Friday night and Kasabian on Sunday, but organizers were keeping quiet about Saturday's top spot, filled last year by the Rolling Stones in their first ever appearance at Worthy Farm.
"We've got it all booked, it was all confirmed a couple of weeks ago — it's purely that we can't give it to you yet," said Emily Eavis, whose father Michael Eavis founded the festival in 1970.
Speaking to BBC radio, she said it was a "massive relief" to announce the main lineup of some 90 acts, although a few of the names had been released previously.
Tickets for the 135,000-capacity event sold out in October in record time — 1 hour and 27 minutes — although any unwanted tickets will be resold this month.
This year's lineup includes the usual mix of rock, electronic, folk and alternative acts, both established names and up-and-coming artists from around the world.
American rock band Pixies will be returning for the first time in 25 years, something Eavis said was a "long time coming."The band apparently feel the same, tweeting: "HEY! GLASTONBURY... For the first time since 1989, we can not wait to see you again."
Glastonbury, which renewed its 10-year license last month, is also keen to support British talent, and giving a top slot to Kasabian is a big coup for the English rock band."Headlining the Pyramid stage glastofest 2014 "First on, Friday 2004, Last on, Sunday 2014". Sergio x," they tweeted.
They join names such as Blondie, Lilly Allen, De La Soul, Goldfrapp, Jake Bugg, Lana Del Ray, Disclosure and Rudimental."People like Disclosure and Skrillex will be taking big headline slots for the first time. It's really exciting," Eavis said.
Jack White was also a "really big deal," she said, adding: "He's got a history here that goes way back. It means a lot to us. It will be just right."