Three males and two females in a Toyota died of their injuries. They were all aged between 16 and 18 years old from the Doncaster area.
The Toyota and a Seat crashed last night in Conisbrough, near Doncaster.
A 21-year-old man believed to be driving a third vehicle was arrested on suspicion of dangerous driving, the BBC reported.
Police said the man, from Doncaster, was later released on bail.
Four of the teenagers in the Toyota were students at Danum School in Doncaster.
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"To a certain degree it's pretty unbelievable that five young people have lost their lives in an incident like this."
The scene of the crash is just 100m from the site of a collision in which three teenagers were killed in 2011.
Serhatlic said it was too soon to tell whether excessive speed or the foggy conditions played a part in the crash.
Formal identification has not yet taken place.
The driver of the Seat, a 45-year-old man from Mexborough, suffered a broken leg.