Lehlohonolo Majoro netted the only goal of the game in the 81st minute to pile more misery on the Team of Choice, who had a completely new technical team on the day.
Eric Tinkler and Vincent Kobola led the Pietermaritzburg-based side from the technical bench but the two coaches weren't able to master a win over Gavin Hunt's team.
After a goalless first half, Wits upped the ante in the second period and punished the visitors after a comedy of errors from the defence allowed Majoro to round goalkeeper Richard Ofori and slot the ball into an empty net.
Majoro won his side a penalty in the closing stages of the game, but Ofori came to the rescue to keep the scoreline respectable.
A slow start to the first half meant both sides had to dig deeper in order to secure all three points on a chilly night in Braamfontein.
For Maritzburg United though, this was always going to be a very tough encounter as they had failed to score in any of their last seven away matches in the league - their longest run this season.
While Tinkler was expected to bring a new sense of belief among the players, Wits knew how to contain their visitors as birthday boy Buhle Mkhwanazi marshalled his defence well from the start.
Thabang Monare and Cole Alexandra also pulled the strings in midfield and therefore made life very difficult for the likes of Siphesihle Ndlovu.
With both sides struggling to create clear-cut chances midway through the first-half, Maritzburg United knew that the longer they held on the more Wits would be frustrated simply because they had never lost any of their Friday fixtures in the last 10 league matches six wins and four draws - while managing to keep five clean sheets.
The scoreline was 0-0 after the first 45 minutes, and Hunt looked very frustrated on the touchline as his team needed the three points to move further away from second-placed Orlando Pirates.
The second half then followed, and Maritzburg United appeared to be having Wits against the ropes in the early stages.
Tinkler then had to take out Fortune Makaringe around the 60th minute. The midfielder didn't have the legs after playing 120 minutes in the Nedbank Cup loss to Witbank Spurs.
At this stage, Wits used Elias Pelembe's pace to penetrate the visitors' defence and play those dangerous crosses into the box.
Credit though must go to Ofori, who played as a sweeper for the better part of the game and produced some match-winning saves to keep Maritzburg United in the game.
However, he was bound to make mistakes and it wasn't surprising to see Majoro round him with ease to open the scoring following a defence-splitting pass by Pelembe in the 80th minute.
This was certainly not what Tinkler and his charges had hoped for, especially because they were so close to snapping their losing streak.
Things went from bad to worse in the space of seven minutes as Majoro won a penalty for his side, but Ofori denied the former Bafana Bafana man as he dived to his right for a fine save.
Nonetheless, it was too little too late for Maritzburg United to at least salvage a draw as they couldn't even threaten Darren Keet, who kept his ninth clean sheet of the season.
Wits are now sitting on 37 points from 19 league matches, their second best tally at this stage of the season since the teams were reduced to 16.
Surprisingly, Wits could only manage 36 points all-season in the previous campaign, meaning they can now be regarded as genuine title contenders, while Maritzburg United remain 16th on the log with only 11 points to their name.