The victory took Amakhosi to third spot on the league table, while the Team of Choice slip down to fifth spot on the standings after tasting their first defeat of the season.
Chiefs coach Steve Komphela made only one change to the starting line-up that faced Bidvest Wits in a PSL match which ended in a 1-1 stalemate last weekend.
Khotso Malope replaced fellow central midfielder George Maluleka, who is out nursing a thigh injury, while Gustavo Paez spearheaded the Amakhosi attack.
Maritzburg coach Fadlu Davids fielded a strong team with in-form attacking midfielder Lebohang Maboe starting behind the main striker Evans Rusike.
The Team of Choice went into the match undefeated in the league this season having recorded two victories and two draws, while Amakhosi had lost one, won one and drawn two.
The hosts were the better side in the early exchanges with Yazid Atouba forcing Chiefs goalkeeper Itumeleng Khune into a brilliant one handed save from a deflected free-kick.
However, Chiefs looked dangerous on transition with Siphiwe Tshabalala orchestrating the visitors' moves just in front of the two holding midfielders, Malope and Willard Katsande.
The deadlock was broken in the 13th minute with veteran attacker Tshabalala involved in the build-up and Paez fired home from close range to make it 1-0 to Chiefs.
This after the Team of Choice had failed to clear the ball away and they had to find a way to beat Khune, who has been recalled into the Bafana Bafana squad.
The visitors continued to play their exciting enterprising football and they were able to test the experienced shot-stopper from range several times.
Cameroonian attacker Atouba saw his long range effort saved by the keeper, who then punched away Rusike's free-kick after failing to hold on to the Zimbabwean's intial attempt.
A few minutes later, Khune continued his goalkeeping heroics as he produced a fine low save to deny Deolin Mekoa to ensure that the first half ended with Chiefs leading 1-0.
The Team of Choice continued their dominance in the second half with Atouba, who joined the KwaZulu-Natal terrorizing Amakhosi's defence with his educated left-foot.
But Chiefs were still dangerous on the counter-attack and they punished Maritzburg, who were left vulnerable at the back at times.
Venezuelan marksman Paez hit the back of the ball to make it 2-0 to Chiefs in the 59th minute after the ball fell kindly for him in the box following Tshabalala's corner.
With Maritzburg attacking in numbers, Komphela made a tactical change - pullling out midfielder Wiseman Meyiwa for defender Erick Mathoho.
Mathoho brought stability in the Chiefs defence, but Lorenzo Gordinho handled the ball in the box and Maritzburg were awarded a penalty in the closing stages of the match.
However, Khune, who was deservedly named man of the match, pulled off a great save to deny Rusike from the spot-kick and Chiefs held on to win 2-0 in Pietermaritzburg.