Man of the match Maluleka volleyed in a beautiful opening goal early in the second half before crowning a good performance with a peach of a free-kick in the 90th minute.
Stars created the better chances in the first half but could not make them count, while Chiefs had a few openings too but were also unable to make the breakthrough.
Dikwena created the first chance when Tintswalo Tshabalala's glancing header from Vuyo Mere's set-piece delivery forced Itumeleng Khune into a diving save after 20 minutes.
From the resultant corner, Robert Ng'ambi then rattled the frame of the goal with a volley that left Khune beaten.
Four minutes later Ndumiso Mabena wasted a glorious opportunity to score when he found himself in behind and one-on-one with Khune, who had come off his line. All he needed to do was lob the onrushing keeper but instead he blazed his shot over the bar.
In the 34th minute Solomon Mathe was played in behind the Chiefs defence but misjudged the flight of the ball and instead kicked the onrushing Khune square in the chest, receiving the first booking.
Five minutes before half-time Maluleka wasted a good opening when Reneilwe Letsholonyane played him into space down the right, but he sidefooted well over the bar when perhaps he should have crossed for Kingston Nkhatha.
Mandla Masango then made a good run to the near post to get onto the end of an accurate Siboniso Gaxa cross from the right but could only direct his header straight at Siyabonga Mpontshane in the Stars goal.
Mabena was stretchered off the pitch with a head wound just before half-time but was bandaged up and resumed the second half.
Five minutes after the restart Chiefs took the lead when, from Masango's corner, Nkhatha's header was cleared off the line by Luvolwethu Mpeta, but the ball dropped to Maluleka, who hit it first time with a sweet volley into the bottom-left corner.
Letsholonyane missed a sitter in the 75th minute that would would have made the game safe. Masango broke into the box down the left before squaring to the central midfielder, who could only tap it high and over the bar instead of into the net.
In the 85th minute it could have been 1-1 as Mpeta missed a glorious chance. Nduduzi Nyanda skinned Masilela down the right and found Mpeta at the back post with a whipped-in cross, but the left-back could not keep it down and tap it in.
And Stars' missed chances came back to haunt them at the death when Maluleka curled a beautiful free-kick in off the left upright from close to 30 yards out to give Chiefs a two-goal cushion heading into the second leg at home.
