The car hit the sport utility vehicle (SUV), which was parked after a tyre burst, on Tuljapur-Pandharpur road at Haglur village, around 4.30 am, an official in-charge of the Solapur rural police station said.
The passengers of both the vehicles were heading towards Solapur, located over 400 kms from Mumbai, after attending a religious event in Aurangabad, he said.
Following the mishap, the 12 victims from both the vehicles were rushed to a state-run hospital in Tuljapur where five of them were declared dead, the official said.
The seven injured people were undergoing treatment in the hospital, he added.
The Solapur rural police has registered a case in connection with the accident.