The 27-year-old's future at Ewood Park has come under scrutiny in recent days following his exclusion from Saturday's 3-1 win over Fulham.
Manager Steve Kean claimed that the centre-back was suffering with a virus and went on to say that Samba was not for sale.
However, it now appears that Kean may have to concede defeat in his bid to keep the former Congo international with the Lancashire-based club.
"I have today officially requested a transfer from Blackburn Rovers Football Club. I have personally informed the owners, manager and executives at the club that I want to leave in this transfer window," Samba said in a statement.
"In my five years at Blackburn Rovers Football Club I have always given 100 per cent in every game I have played. I have had several opportunities to leave but I have always stayed.
"I have decided now is the right time for me to pursue a new challenge and I have asked the club to respect my decision and allow me to leave. I thank the fans for their support and I hope they feel I have served them and their club well."
Queens Park Rangers, Tottenham Hotspur and Paris Saint-Germain are all reportedly interested in adding Samba to their squads.