The best chance of the first half was created by striker Michelle Katsvairo in just the second minute of the game as he stole the ball off defender Bevan Fransman but then missed the target one-on-one against goalkeeper Bongani Mpandle.
It was an evenly contested game with Maritzburg creating arguably the better chances in the first half, Amakhosi’s next best attempt being a disappointing Hendrick Ekstein shot over the bar from the edge of the area.
Ernst Middendorp's side also had a strong penalty appeal waved away when Kgotso Moleko handled in the area while lying on the ground, while late in the game Moleko also escaped a red card when the referee failed to spot his headbutt on Blessing Moyo.
Itumeleng Khune had to bail out his centre-back Erick Mathoho in the 31st minute when the Bafana Bafana international was dispossessed in his own area by hungry young striker Luyanda Ntshangase. Khune came out and spread himself wide, taking one in the face for the team.
Three minutes later Khune was called into action again as he produced a brilliant diving, fingertip save to keep out a thunderous long-range drive from Dennis Weidlich as the ball cannoned back off the upright.
Chiefs were fortunate not to go behind just before half-time when Maritzburg bundled the ball goalward but Lorenzo Gordinho was on the line to clear the danger.
Early in the second half Steve Komphela's side showed more ugency to get a goal but were unable to fashion any more clear chances, with Lebese failing to test Mpandle with two attempts and Sibusiso Khumalo stinging his palms with a shot from a tight angle.
Khune had to be alert in the 66th minute to produce an acrobatic save to keep out Weidlich once again. The defender was somehow unmarked in the box at a corner but watched as his volley was tipped over the crossbar.
Chiefs' best chance of the second half fell to Ekstein in the 70th minute when William Twala found him unmarked at the far post, but Ekstrein got the finish all wrong as the ball bounced comically wide off his knee.
Thunder and heavy rain started to come down at FNB Stadium and the game looked to be heading to extra time until the 83rd minute, when the stadium's floodlights went out, forcing a temporary suspension.
When play eventually resumes following varius stadium security checks, neither side could create any further chances as they looked to break the deadlock, and the game went into 30 minutes of extra time, during which there were no goals.
Chiefs kept their nerve in the shootout after Kurt Lentjies struck the post with the first spot-kick, and Keagan Buchanan slotted home the winning penalty as Amakhosi won the tiebreaker 4-2.