The Chinese national was driving a southbound grey Ford Ranger ute when it collided head on with a black Holden Cruze station wagon about 4.50pm on Saturday on State Highway 1, north of the Moeraki turn off, police say.
The 5-year-old girl was a passenger in the station wagon and died at the scene.
The other four occupants of the station wagon were family members from Oamaru - a woman (40), a man (41) and two children aged 7 and 9.
They were airlifted by two Otago Rescue helicopters to Dunedin Hospital with serious injuries, and remain in a serious but stable condition.
Three other Chinese nationals were travelling with the man. All four occupants of the ute were taken to Oamaru Hospital by ambulance. Three had minor injuries and have since been discharged, and the fourth, a middle aged woman, remains in Oamaru Hospital with moderate injuries.
The 32-year-old Chinese man will appear in the Dunedin District Court today on one charge of dangerous driving causing death and four charges of dangerous driving causing injury.
Southern District Command Centre co ordinator Senior Sergeant Ben Butterfield said police expected to release the name of the 5-year-old girl later today.
Sergeant Tony Woodbridge, of Oamaru, said it appeared one of the vehicles had veered into the wrong lane between the Moeraki township and the Moeraki Boulders turn offs.
The police serious crash unit was investigating, he said.
Police would like to speak to anyone who had seen the accident, or seen either of the vehicles involved prior to the crash.
Sgt Woodbridge thanked motorists for their patience on Saturday afternoon.
''The public were very good with the delays when they knew how serious it was,'' he said.
''A crash like this hurts a lot of people. It's very sad, and police thoughts go out to the family.''
State Highway 1 was closed for more than two hours. A farmer opened an unofficial detour through his property, for light vehicles only.
The highway was reopened to one lane by about 8pm, and both lanes reopened at 9pm.
