Bafana started well and almost created some early chances as they forced the Mali defence into making mistakes.
Bernard Parker tried to get a shot away in the fifth minute but it was blocked before Tokelo Rantie shouted for a penalty after a slight tug in the area but the referee waved his claims away.
Seydou Keita went close in the eighth minutes with a cracking strike from the edge of the area that whistled just off target.
Reneilwe Letsholonyane was presented with a chance to shoot after good work from Rantie soon after but the Kaizer Chiefs man took too long on the ball and the Mali defence closed the gaps.
Thuso Phala then whipped a superb cross into the area but it was just ahead of May Mahlangu who saw his glancing header sail wide.
Rantie would be denied a clear route on
goal by a last-ditch challenge from Adama Tamboura while Adama Coulibaly nodded well wide in the 19th minute.
Soumaila Diakite pulled off a great save to deny Rantie's dinked effort after he was played in by Mahlangu in the 21st minute while the Eagles were forced into an early substitution after Samba Diakite was replaced by Sigamary Diarra.
Tamboura then saw his swerving effort test Itumeleng Khune but Bafana would grab the lead after a swift move ended with Phala scuffing a low pass to the far post where Rantie was free to tap in.
The goal scorer suffered a knock earlier in the game though and eventually had to come off to be replaced by Lehlohonolo Majoro.
Samba Sow had a great chance in the 42nd minute to equalise when the ball was pulled back to him at the edge of the area but he blazed his effort well over while Dean Furman made a telling block to block Sigamary Diarra late in the half as Bafana held onto the lead.
Bafana seemed to take their foot off the gas slightly after the break as the Eagles slowly came into the game but Majoro had a great chance in the 56th minute when he was slipped in by Letsholonyane but his touch was poor and the goalkeeper made the save at his feet.
The visitors would punish that miss moments later when Samassa curled the ball into the middle and Keita was left free to head at goal from close range. Khune got something on the ball but it was not enough as it bounced over.
Mali could have had a second minutes later as Siboniso Gaxa played a poor pass back toward Khune and Mahamadou Samassa pounced but the goalkeeper made a superb save.
As the half wore on, pace dropped from both sides considerably but the brilliant Mahlangu would test the goalkeeper with a low strike from the edge of the area.
Neither side wanted to make a mistake in the dying minutes of regulation time and no real chances arrived as the game went to extra-time.
Bafana had to scramble the ball away from an early free-kick while Mahlangu burst forward on the counter but sent his strike straight at the goalkeeper.
Chances were hard to come by as extra-time stretched on and legs began to tire, and penalties were needed to decide matters.
Siphiwe Tshabalala took the responsibility to take the first penalty and made no mistake but both Furman and Mahlangu had their efforts saved before Majoro curled a horrible effort wide of the target as Bafana crashed out.
Standard Bank Moment of the Match: Tokelo Rantie tapped in at the far post to give South Africa the lead after a positive first-half but the tournament hosts would end up tumbling out after losing in a penalty shootout.
Bafana: Itumeleng Khune, Siboniso Gaxa, Bongani Khumalo, Siyabonga Sangweni, Tsepo Masilela, Bernard Parker, May Mahlangu, Dean Furman, Reneilwe Letholonyane, Thuso Phala, Tokelo Rantie.
Mali: Soumaila Diakite, Fousseni Diawara, Adama Coulibaly, Molla Wague, Adama Tamboura, Mohamed Sissoko, Samba Sow, Seydou Keita, Samba Diakite, Mahamadou Samassa, Modibo Maiga.
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