Megan Salt, aged 74, and her husband Barry Salt, 73, from the Wednesbury area, both died in hospital following the collision near Stone in Staffordshire on Sunday.
Mr and Mrs Salt were travelling in a grey Ford Grand C-Max when the collision happened at around 4.45pm on the A34 in The Fillybrooks.
A 17-year-old girl who was in the car with them was unhurt, Staffordshire Police said.
The second car involved was a black Mercedes AMG A-class.
A man and a woman who were in the Mercedes were also taken to hospital with serious injuries.
The man, aged 29, has since been discharged from hospital and is said to be helping officers with their inquiries. However the 24-year-old woman remains in hospital in a stable condition.
Staffordshire Police said that Mr and Mrs Salt's family have requested that their privacy be respected as they come to terms with the deaths.
The coroner has been informed.
Anyone who witnessed the crash or who may have dash-cam footage or information that may help investigators should contact Staffordshire Police on Facebook, Twitter, or call 101, quoting incident number 451 of January 16.
Alternatively email the force's collision investigation unit directly at email@example.com.