Opposition parties, trade unions and many churches have called for a boycott of the much-delayed system, saying it is unfair because South Africans already pay a fuel tax, VAT and existing tolls while arguing that Sanral's system is badly designed.
Several court victories allowed it to go live on Monday.
The system affects the ring road around Johannesburg and the motorway to Pretoria, with South Africa's government saying the toll is needed to pay for improved roads.
According to local reports, road users have been finding alternative routes.
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