The game had ended in a scoreless stalemate after extra time at the Newlands Stadium on Sunday afternoon.
For the most part of the first half, and indeed the entire game, it was Chiefs who had the upper-hand, Santos only having a few early chances as Jurie Basie fired in from a tight angle and then bounced a header over the bar.
The visiting side had a 14th minute chance when Jimmy Tau cut in from the right, but fired straight at Lee Langeveldt.
In the 23rd minute AmaKhosi were within a whisker scoring when Knowledge Musona’s header from a corner-kick struck the crossbar.
The Soweto giants maintained their superiority in attack for the remainder of the half, but only had shots from Thabang Rooi and Mandla Masango, both which flashed over the bar, to show for their efforts.
As Chiefs controlled the tempo of the game and Santos looked to make things happen on the counter-attack, chances remained rare in the second stanza.
The game however burst to life in the final 10 minutes of the game.
Chiefs should really have wrapped the match up during this period but poor finishing, especially from Musona, meant the score remained at 0-0 as the clock reached the end of regulation time.
Both teams had their chances in extra time, but the score remained goal-less at the end, sending the tie into penalties
Both Phikolethu Spelman and Ricardo Skippers skied their penalties over the bar, leaving Abia Nale to seal the win for Chiefs with a coolly taken spot-kick.