A single goal from Khumbulani Banda, his first touch of the game, nine minutes from time handed the Amakhosi only their second loss of the season.
Chiefs were the better side for most of the first half, but their decision making in the final third was poor and chances on goal were at a minimum.
Instead, the first shot on goal came at the other end of the park in the 17th minute after a mistake by Willard Katsande allowed Thamsanqa Mkhize to control a right wing cross on his chest, but he volleyed wide from six-yards out.
A minute later Chiefs had their first significant shot on goal when Siphelele Mthembu showed good strength on the edge of the box before turning and let rip, but his low effort went inches wide.
The second half saw Chiefs start the better of the two teams, with a pin-point cross from Bernard Parker met by Tefu Mashamaite in the 52nd minute, but he headed over from close range.
Eight minutes later Parker worked himself into space on the edge of the Maritzburg box, but his low shot skimmed the wrong side of the post.
Substitute Banda changed the face of the game with his first touch in the 81st minute after he headed home a corner-kick to give Maritzburg the lead.
Chiefs tried to get back into the match and came close in the 93rd minute when an overhead-kick from Siboniso Gaxa struck the woodwork.
The result, combined with Mamelodi Sundowns’ 5-0 thumping of Polokwane City, sees Chiefs’ lead at the top of the table reduced to eight points.
The win for Maritzburg sees them into eighth place on the League table with 27 points from 22 games.