The Golden Arrows mentor earned 20,259 votes, securing his place on the bench for this year's highly anticipated showdown.
Mngqithi succeeds Jose Riveiro, who successfully guided the All Stars in the previous two editions.
Under the Spaniard, the All Stars built a reputation for upsetting the Carling Knockout Cup champions, defeating Stellenbosch FC 2-1 in 2024 and cruising past Magesi 3-0 last season.
In the 2024 encounter, Mfundo Vilakazi and Ashley du Preez scored for the All Stars before Mervin Boji's late response for Stellies.
A year later, the team produced an even stronger display, with Naledi Hlongwane netting a brace and Samkelo Zwane adding a third to seal a comfortable win.
This year, Mngqithi will aim to extend that proud record when the All Stars face newly crowned Carling Knockout Cup champions Orlando Pirates. The fixture will take place at Moses Mabhida Stadium on Saturday, kicking off at 15:00.
Mngqithi will not handle the occasion alone - Champion Coach Bonginkosi Chonco will join him on the sideline as part of the Carling tradition that gives supporters a voice in team selection and leadership.
With momentum and history on their side, the All Stars will look to make it three consecutive victories against the champions in what promises to be another spectacle for supporters.
Mamelodi Sundowns will look to strengthen their challenge for the Betway Premiership crown when they host Golden Arrows at Loftus Versfeld Stadium on Wednesday.
Golden Arrows missed an opportunity to move into the top half of the Betway Premiership on Saturday, while Siwelele beat TS Galaxy, and Orbit College drew with Richards Bay.
The league action heats up this weekend with eight teams fighting for points on different sides of the table, as some target the top eight and others avoid the drop.
The PSL has officially confirmed the dates and venues for the quarter-finals of the Nedbank Cup.
