Kambli was taken ill while he was driving from Chembur to Bandra and suddenly stopped the vehicle.
A policewoman on duty, Sujata Patil noticed he could not drive and arranged to rush him to Lilavati Hospital.
Hospital sources say he is under observation and undergoing various tests to determine his health condition. He is being treated by a cardiologist Dr. J.P. Jadwani.
Vinod Kambli shot to fame in 1988 when he shared a then world record 664-run partnership with Tendulkar in an inter-school match in Mumbai, with both batsmen making unbeaten triple centuries.
While Tendulkar retired earlier this month as the world's leading run-maker in both Test and one-day cricket and an unprecedented 100 international centuries against his name, Kambli faded after a bright start.
The flamboyant left-hander hit two double-centuries and two hundreds in his first eight Test innings after earning a debut in 1993, but another three-figure knock in Tests eluded him.
Kambli played the last of his 17 Tests in 1995 before he had turned 24, finishing with 1,084 runs at an average of 54.20.
He also scored 2,477 runs in 104 one-day internationals with two centuries.