Sam Smith and George Ezra are also among the first wave of acts confirmed on the line-up.
Other names on the bill for the festival, which will take place on 22 and 23 August, include Ellie Goulding, Radio 1's Annie Mac and Olly Murs.
V Festival, which is now in its 20th year, will again take place at Weston Park in Staffordshire and Hylands Park in Chelmsford.
Calvin Harris will play at Weston Park on 22 August and in Chelmsford the following night. Kasabian will start in Hylands Park before heading to Staffordshire on 23 August.
Kasabian guitarist Sergio Pizzorno, said: "V is for victory, V is for voodoo, V is for vacuum cloud, V is for very very very very excited. See you in the fields."
Hozier, Fuse ODG, Labrinth, Clean Bandit, Ella Eyre, Stereophonics and Chrvches are also on the bill as well as Ella Henderson, The Proclaimers, Sir Tom Jones and Grandmaster Flash.
Festival Director Simon Moran said: "We wanted to champion British talent at this year's festival and with the likes of Calvin and Kasabian leading the way we don't think it'll disappoint.
"The eclectic mix of established artists and rising stars, with a few more in the pipeline, means that once again there is something for everyone at V Festival."
Justin Timberlake and The Killers headlined the festival last year.
More names across four stages will be announced in the lead-up to the festival.
See the full line-up.
Tickets for V Festival 2015 go on sale on 6 March.
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Calvin Harris and Kasabian will headline this year's V Festival.