A youth product of Lokomotiv Sofia he spent three seasons in the Bulgarian A Group with the first team before switching to Dynamo Kyiv, winning six major honours with the Ukrainian club.

Peev was discovered at the age of 21 by Dynamo Kyiv manager Valery Lobanovsky, while playing for Lokomotiv, and signed for €2,5 million.

[1] In 2008, he was chosen the fans favorite player of the Russian Premier League and received a rare revolver from 1936 used by the Red Army.

[2] A right back or right winger known for his pace and attacking attitude, he was part of the Bulgarian 2004 European Football Championship team who exited in the first round, finishing bottom of Group C, having finished top of Qualifying Group 8 in the pre-tournament phase.

On 10 May 2010, following his strong performances for his club team, Peev was recalled to the national side for the friendly match against Belgium.