He played youth football for Charlton before joining Aston Villa, where he made almost 200 appearances between 1999 and 2007.
"At around 7.55am (0655GMT) police were called following reports of a collision involving a van and a Range Rover", said a statement from Cheshire Police.
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He collided with an oncoming vehicle, the association added.
Bolton Tweeted "Everybody associated with Bolton Wanderers Football Club is deeply saddened to learn of the passing of our former defender, Jlloyd Samuel".
Stan Collymore paid a heartfelt tribute to his former team-mate, who he described as a fantastic pro.
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"Rest in peace, Jlloyd".
The thoughts of everyone at the72 are with the friends and family of Jloyd Samuel at this time.
Samuel is survived by his wife Emma and three children - Javarne, Lakyle and Amara - who have been informed of the devastating news.
Samuel finished playing top-level football in England back in 2011, moving to Iran, but returned to play non-League in Cheshire as recently as this season.
Villa said in a statement: '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 statement detailed that Samuel's body was "discovered burnt" after the crash, and extended the "deepest condolences" to the player's family.
"Our thoughts are with his friends and family at this incredibly hard time".