Fourteen suspects believed to be part of a syndicate are expected to appear in the Stellenbosch Magistrates Court on Thursday.
The group will face charges of fraud, theft and money laundering exceeding R40 million.
According to police, the alarm was raised by a local financial institution about the syndicate operating a huge asset financing scheme involving vehicles.
It is alleged that the suspects would create and submit false vehicle finance applications to motor dealerships with whom they had corrupt relationships.
A multi-disciplinary task team was set up and two women and 12 men were arrested in the early hours of Wednesday morning.
The accused spent the night in prison and will make their first appearance on Thursday.
Police say the investigation is ongoing and more arrests are possible.