The accident happened on the A253 Canterbury Road West, in Cliffsend, near Ramsgate, on Tuesday afternoon.
The 57-year-old driver of a Ford Fiesta died from her injuries at the Queen Elizabeth The Queen Mother Hospital.
The family in the other car, a Ford Mondeo, were treated in hospital for non life-threatening injuries.
The father suffered back, neck, shoulder and leg injuries while the mother, seven-year-old girl and 10-year-old boy suffered seat belt injuries.
Three of the family have been detained in hospital.
Four ambulances attended the scene.
South East Coast Ambulance Service medic Andy Smith said it was a "very horrible" accident and praised crews for their rapid treatment of the injured.
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