Music
Rex Features
The 'Heart Of Gold' singer will top the bill on June 27, a day before Bruce Springsteen heads up the same stage for a sold-out Hyde Park show.
Other bands announced for Hard Rock Calling include Fleet Foxes, The Pretenders and Seasick Steve.
Chrissie Hynde of The Pretenders said: "We would play a garden shed to be on a bill with Neil Young but Hyde Park - summer - with 'The Loner'?
"This is what makes a thousand hours on tour buses all worthwhile. This is why people get in bands."
Tickets for the second day of the festival go on sale on March 13 at 9am.
Neil Young was recently confirmed as the final headliner of the Glastonbury Festival, which takes place over the same weekend as Hard Rock Calling.
He has also been booked to play the Isle of Wight festival earlier in June.
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