He supported the Rolling Stones in Vienna and was invited to appear with them again at the Don Valley Stadium in August 2006 and was also booked to appear at the V Festival and The Austin City Limits Music Festival, Texas, later in 2006, with a European tour in the autumn.
In May 2006, Nutini also played at BBC Radio 1's Big Weekend in Dundee.
He later worked as a studio hand at Glasgow's Park Lane Studio.
It was here, where he started demo-ing songs, writing with Jim Duguid and the drummer of Speedway.
Nutini performed at the Glastonbury Festival in June 2007 on the famous Pyramid Stage on the second day of the event.
Nutini also performed at the British leg of Live Earth at Wembley Stadium on 7 July 2007, with his set including a cover of "What A Wonderful World", a classic pop tune by Bob Thiele, George David Weiss, and George Douglas.
Caustic Love debuted at number one on the UK Album Charts and was certified platinum by the BPI in June 2014.
He was first encouraged to sing by his music-loving grandfather, Giovanni "Jackie" Nutini, and a teacher at his school, St Andrews Academy, who recognised his talent.
In July, he appeared on Friday Night with Jonathan Ross, performing "Coming Up Easy".
This was released as the second single to the album on 10 August and it debuted at number 62 in the UK Singles Chart on 16 August 2009.
On 1 June 2009, Nutini released his second studio album Sunny Side Up, which debuted at number one.
The first single from the album "Candy" was released on 25 May.
On 10 September 2009, Nutini performed "Coming Up Easy" on The Tonight Show with Conan O'Brien.