With the match evenly poised and crying out for inspiration, Venter obliged with a screamer on 72 minutes to send the Goble Park crowd into delirium.
It was a pretty scrappy affair at best as the two sides, meeting for the second successive Saturday at the same venue, went about their business warily fearful of making costly mistakes.
Wits edged the contest in Stars in terms of shots on goal and shots on target, but the visitors were made to pay for profligacy as Venter delivered the sucker punch..
Both sides battled to create any real goal-scoring chances and the first half was largely devoid of any real goalmouth action.
Jabulani Shongwe did fire an early header just wide of the mark, but the rest of the half was a scrappy affair as both sides conceded a several free kicks in midfield.
The second half started in similar fashion and it was an even contest until Free State Stars found the breakthrough with a bit of magic on 72 minutes. Venter received the ball in some space and had a go at goal, finding the back of the net with a screaming effort from range.
The goal livened things up and Wits came close to finding a leveller on 80 minutes as Onismor Bhasera flashed one wide of the mark from inside the area.
And the goal would prove to be the winner as Ea Lla Koto booked their place in the quarter final of the Telkom Knockout.