The Sky Blues were the 39-year-old Zimbabwean's first English club after he was spotted playing for Highlanders in his homeland, moving to the midlands in 1991 and staying with the club until 1997.
A statement from the npower League One club read: "Coventry City Football Club is saddened to hear of a tragic road accident in Zimbabwe that has left former striker Peter Ndlovu in a critical condition and claimed the life of his brother Adam.
"It has been reported that both were travelling from an away match between Chicken Inn FC and a local side when Ndlovu's car suffered a tyre blow-out which caused the car to veer off the road 20 kilometres outside Victoria Falls.
"Ndlovu achieved iconic status during his six years with the Sky Blues where he netted 39 goals in 176 (league) appearances for the club.
"Coventry City sends its best wishes and condolences to the Ndlovu family who will be in our thoughts."