BackpagepixIqraam Rayners was named Man of the Match after producing an eye-catching display at Old Peter Mokaba Stadium.
It was an important result for Stellenbosch who reached the semi-finals of the League Cup for the first time in the club's history.
For Polokwane, it was the end of their ambitious campaign which saw them convincingly eliminate SuperSport United in the Round of 16
BackpagepixWith four minutes into the contest, Stellenbosch felt they deserved a penalty when Jayden Adams was fouled inside the box by Lebohang Nkaki.
But referee Sikhumbuzo Gasa waved play on and it was not long before the visitors grabbed their first goal.
BackpagepixRayners thrust Stellenbosch ahead when he coolly slotted in an Adams feed in the seventh minute.
The goal pumped up the Cape Winelands outfit while Rise and Shine appeared frustrated.
It proved to be a major turning point in the game.
BackpagepixAs they tried to adjust themselves and settle into the game, Rise and Shine were haunted by an injury to defender Bulelani Nikani.
They were forced to make a substitution as early as the 12th minute and came Francis Baloyi to replace Nikani.
The hosts had to change their game plan with a new man at the back and with their captain Nikani now out.
BackpageThe departure of Nikani seems to have negatively affected Polokwane City as things immediately went south for the hosts.
The home side's defence was caught napping, letting Titus break loose and come to the end of goalkeeper Sage Stephens' long ball - making it 2-0 to Stelies.
He easily beat Manuel Sapunga in goals for Polokwane City.
BackpagepixKgaogelo Sekgota had opportunities to increase Stellenbosch's lead but was wasteful especially when he fired wide a pass from Rayners early into the second half.
It was a disappointing outing for the former Kaizer Chiefs winger who arrived in the Cape Winelands from Amakhosi with so many expectations on him.
BackpagepixPolokwane put some trust in veteran forward Ndumiso Mabena but he failed to come to the party.
Their hopes of a comeback started fading as the match drew to a close.
It turned out to be a difficult evening for Mabena who played the entire match.
BackpagePixStellenbosch held on to their two-goal lead, giving their hosts little chance of a comeback.
Stellies defended well and in the end, emerged victorious as Polokwane City put some pressure but it did not pay-off.
Rayners walked away with the R100,000 Man of the Match cheque.