The retired midfielder has replaced Daniel 'Dan' Malesela, who has reportedly been fired by the Chilli Boys three games into the new season.
The Chilli Boys registered two defeats against Orlando Pirates and Baroka FC, one victory over AmaZulu in the PSL under Malesela's guidance.
Siviwe Mpengesi, the Chippa club chairman, is said to have decided to fire Malesela after the team's 3-1 home defeat to Baroka on Tuesday.
The former Mamelodi Sundowns captain has now been replaced by Moloi, who is expected to serve as the caretaker coach.
Moloi, who has worked for Pirates as an assistant coach, is back at the Chilli Boys having served as the Malesela's assistant prior to the current season.
But the former Bucs midfielder quit after a month and he informed the media that Malesela wanted a learning assistant hence he decided to leave the club.
United made the announcement on their official Twitter page: