The men, who were arrested between the end of October last year and the beginning of November, face charges of attempted murder and armed robbery.
They were all in their 20s and were arrested in their homes in an informal settlement in Emalahleni, Mpumalanga.
Mthembu was attacked while withdrawing money from an ATM in Mandela Street, Emalahleni, on October 19 last year.
He was approached by an armed man and several others who demanded that he withdraw all his money from his account.
A scuffle ensued and Mthembu was shot. The bullet grazed his cheek and hit him in the shoulder.
He was hospitalised for 10 days and was booked off work until the end of November, 2014.