Joshua Sauls and Khethukuthula Zwane had twice given Spurs the lead at the Puma Rugby Stadium, but a brace from Yannick Zakri forced the match went to extra time and penalties.
Maritzburg started well and had a chance when Mxolisi Kunene picked the ball up from a short corner in the 10th minute before beating a man, but his parting shot was dragged wide.
Just five minutes later United were instead to find themselves a goal down as Joshua Sauls slotted home a cross from Bonginkosi Nkosi.
The Team of Choice fought back and found the equaliser just five minutes later as Zakri tapped in from close range after a mistake in the Spurs defence.
It was not long however – just three minutes, before United found themselves behind again; Khethukuthula Zwane restoring the hosts’ lead with a 23rd minute header.
Maritzburg had good chances before and after the interval to score, but Thabiso Kutumela fired over the bar in the 35th minute after being supplied by Bandile Shandu, before Fortune Makaringe missed a decent chance 10 minutes in to the second half.
Zakri though was in uncompromising mood and he did the business once more for the KZN Capital City club with a well taken header in the 66th minute.
The Team of Choice were close to winning it inside 90 minutes time when Zakri teed up Makaringe, but he was unlucky to strike the post.
Muhsin Ertugral’s men continued to ask questions of the Spurs defence in extra time and Pogiso Sanoka had a shot cleared off the line before hitting the post with a header after a Kunene free kick.
Luck again deserted Maritzburg in the shoot-out as Rushine De Reuck and Miguel Timm failed to convert their spot kicks as the hosts triumphed 5-4.