Amakhosi, who beat Mpumalanga Black Aces 4-0 in the MTN8 last week, prevailed on Saturday via George Lebese's 55th minute goal to hand Stars coach Tom Saintfiet a defeat in his first game in the PSL.
A defensive Ea Lla Koto were not helped by losing the services of new goalkeeper Daouda Diakite with a seemingly serious knee injury on the stroke of half-time.
Chiefs dictated affairs early on in Phuthaditjhaba, with Mandla Masango and George Maluleka testing Diakite with useful strikes, while Kingston Nkhatha fired narrowly wide off a Lebese cut-back midway through the first stanza.
Lebese also had a decent shout for a penalty when he tumbled in the box under a challenge from Angula Da Costa but referee Kulasander Qongqo was unconvinced.
Saintfiet's men were content to sit back and try and catch their opponents on the counter. They nearly succeeded once through Richard Henyekane, but the speedy striker failed to hit the target with a first-time attempt after keeper Itumeleng Khune was pulled out of position when sweeping a dangerous ball over the top.
The hosts then suffered a setback close to the recess, as debutant Diakite sustained suspected ligament damage when taking a goalkick, prompting the introduction of Ayanda Mtshali.
The Glamour Boys made their dominance count 10 minutes after the interval, as Lebese stabbed the ball home from close range following some sloppy defending from Da Costa.
Stuart Baxter's charges continued to set the pace in the latter stages but were unable to beat Mtshali again, who notably foiled a downward header from Nkhatha with 15 minutes to go.