Five Limpopo high school pupils died when the car that they had hitched a ride in crashed along the R574 road between Groblersdal and Mpudulle on Tuesday at around 14:00.
Limpopo Education MEC Polly Boshielo expressed her "deepest sorrow and devastation" following the accident.
The five pupils - four in Grade 10 and one in Grade 9 and aged between 15 and 18 - all attended the AM Mashego Secondary School near Groblersdal.
According to the department, the pupils had been hiking home after writing their Agricultural Science and English examinations.
Sending her deepest condolences to the families, Boshielo said: "We are deeply saddened. Our hearts are heavy and we accordingly send our deepest heartfelt condolences to the families of our learners and the school community.
"This is a very difficult time for all of us, friends and relatives of these learners. We lack the necessary words at this point in time. We must be united in this time of grief," Boshielo said.
According to a statement issued by the department, a psychosocial unit has been dispatched to provide trauma counselling to learners, teachers, support stuff and the bereaved families.
Police in Hlogotlou outside Groblersdal have opened a case of culpable homicide following the incident.
According to police spokesperson Brigadier Motlafela Mojapelo, the driver of a Nissan NP200 bakkie apparently lost control of the vehicle when approaching Matrompi bridge and it rolled several times, instantly killing the five learners and critically injuring the driver and his crew. The injured were taken to hospital.
"The deceased, all girls, were allegedly hitchhiking next to the local filling station and were given a lift by the driver of the said vehicle. They were coming from school to their respective residences at Sephaku and Kgaphamadi villages," Mojapelo said.
They have been identified as Beauty Motsweni and Pearl Rakgalakane from Sephaku; and Lucy Monareng, Chantel Monareng and Karabo Mogoaneng from Kgaphamadi.
Police investigations are continuing.
The scene where 5 pupils died when hitching a ride after writing exams on Tuesday. (Pics: Supplied)