Amakhosi looked destined for victory at the Harry Gwala Stadium after racing to a two-goal lead only for the home side to come roaring back and draw level.
However, Chiefs would have the final say from the penalty spot to earn a valuable three points that keeps the pressure on Orlando Pirates in the battle for the top three on the PSL table.
A breathless first half in Pietermaritzburg resulted in no less than four goals.
Maritzburg only had themselves to blame for going behind as early as the fifth minute when a goalkeeping error at the back led to an easy tap-in goal for Keagan Dolly.
Renaldo Leaner was caught way off his line, allowing Ashley Du Preez to square the ball for Dolly to tap it into a gaping net.
Five minutes later, Chiefs were two up and this time they had their own ingenuity to thank for the goal.
It was a swift counter-attack that led to an opportunity for Christian Saile, who smashed the ball home from long range after the Maritzburg defence had made the mistake of backing off.
Chiefs were flying now but Maritzburg refused to lie down and would soon get a goal back via the head of Mogamad De Goede, who was waiting to latch on to a well-taken corner kick swung into the near post.
The end-to-end action continued and with four minutes to play, Maritzburg scored again, this time thanks to a superbly-taken free kick from their young French striker Amadou Soukouna, who curled a spectacular shot over the wall and into the top corner to level the scores at 2-2.
After all of the frantic action in the opening 45 minutes, the second half wasn't quite as breathless.
Chiefs again started well and applied some pressure on the hosts, but this time Maritzburg's defence stood firm.
A pivotal moment in the match arrived with 20 minutes to play when Du Preez went down in the area and the referee pointed to the penalty spot.
Maritzburg players surrounded the referee in protest but he was unmoved and, after a long delay, it was Yusuf Maart who stepped up to smash the penalty home and put Chiefs back in front.
The home side needed to find a way back but they could not repeat their first-half heroics, as Chiefs hung on for their third straight PSL win.