The singer, who will play a set on the main stage at the events in Chelmsford and Staffordshire on the weekend of August 18-19, described the booking as "unbelievable".
Murs explained: "Well the biggest difference from 2011 to 2012 is that last year I was on the 4 Music stage and this year I'm going to be on the main stage, which is just unbelievable.
"I suppose I'm going to be a lot more nervous this year as the main stage is the one everyone wants to get on. So to finally get the opportunity, I'm just going to buzz off it and have a good time."
Speaking about who he would most like to collaborate with at the event, Murs revealed: "The band I would most like to perform with at V Festival has to be Madness. I've been a massive fan for a long time and I love their music.
"Madness for me would be the perfect combination and I would love to jump on stage with them. I know it will probably never happen, but I'd love to."
The Killers and The Stone Roses have been confirmed as the headliners for V Festival 2012, with further performances coming from Noel Gallagher, Nicki Minaj and Tom Jones.
Tickets for V Festival 2012 go on sale from 9am on March 2.
Watch Olly Murs talk about V Festival 2012 below: