Despite being born in Trinidad and Tobago, Samuel grew up in London, where he joined Charlton Athletic, then moved to Aston Villa in 2007. The former Premier League defender has died at the age of just 37.
The Trinidad and Tobago Football Association said he had "collided with an oncoming vehicle".
A two-time Trinidad and Tobago global, Samuel was an ever-present for Bolton in the Premier League during the 2008/09 season while he also featured in the Trotters' UEFA Cup victories over Red Star and Atletico Madrid the year before.
Aston Villa, who face Middlesbrough in the second leg of the Championship play-off semi-final, tonight, tweeted: "We are deeply saddened to hear of the death of our former player Jlloyd Samuel at the age of just 37 in a vehicle accident". "The TTFA and all his former teammates extends deepest condolences to his family in this most hard time".
A spokesman for the force said: "At around 7.55am police were called following reports of a collision involving a van and a Range Rover near to Costcutter on West Lane".More news: Ga. Senator, Gov. candidate says he's starting 'Deportation Bus' tour for 'illegals'
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The driver of the van, a 54-year-old man, has also sustained serious injuries and is now being treated in hospital. He won two senior caps in total.
He also played for another Iranian club Paykan for one year.
Manchester United's Ashley Young remembered how Samuel had "taken him under his wing" when he started out at Aston Villa.
Absolutely gutted to hear the news of the passing of Jlloyd Samuel. Thoughts with them, his wife Emma, and all his family'. "Rest in peace Jay".
Former Villa player and radio pundit Stan Collymore said: "Devastating news about J Lloyd Samuel".
The thoughts of everyone at the club are with his family and friends at this hard time.