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The death toll from Saturday's accident on the R409 between Ndabakazi and Ngqamakhwe has risen to five.
A spokesperson for Provincial Traffic, Unathi Binqose, says the accident involving a Corsa and Toyota Avanza happened shortly after midnight.
He says three people died at the scene while two more have succumbed to their injuries in hospital.
This brings the total to seven killed in two separate accidents in the Eastern Cape on Saturday.
Binqose says the second accident involved a single vehicle with two occupants overturning on the N2 just outside Mdantsane.