Marumo Marumo appeared in court on Monday on charges of fraud, racketeering, and money laundering, related to electricity theft, the organisation said in a statement on Tuesday.
Operation Khanyisa is a campaign partnership between organisations, including Eskom, Crime Line, and Business Unity SA, aimed at promoting the legal use of power in South Africa.
Marumo would appear in court again on 31 July.
He was arrested following a three-year investigation into the syndicate, which was believed to be managed from the Vaal.
More arrests were expected in the case.
In a similar, though unrelated, case, two people convicted of selling illegal prepaid electricity vouchers were sentenced to a combined 111 years in the South Gauteng High Court in Johannesburg in 2011.
According to Operation Khanyisa, Eskom loses billions of rand in revenue each year through electricity theft, including buying and selling of illegal prepaid electricity vouchers.