Striking the ball with a calm confidence, Ivanovic was in control from first point to last, running out a 60 62 winner against her fellow wildcard.
Ivanovic, who warmed up for her season finale with a runs to the final in Linz and quarterfinals in Moscow, set the tone at the start of the match with a love hold before breaking the Bulgarian with a precise backhand winner one game later.
Despite the best efforts of her compatriots inside the Armeec Arena, Pironkova could find no answer to the early onslaught and after just 22 minutes Ivanovic wrapped up the opening set with yet another forehand winner.
Pironkova belatedly got on the scoreboard at the start of the second, and the roar of approval from the crowd seemed to temporarily inspire her as she carved out her first break points in the next game.
However, this only succeeded in raising Ivanovic to greater heights. Displaying her full repertoire of shots she fended off the danger before promptly breaking to love. It was one-way traffic from then on as the Serb raced towards the finish line, wrapping up victory when Pironkova dumped a forehand into the net.
"It's always tough playing a local girl," Ivanovic, who won the Tournament of Champions at its previous home in Bali in both 2010 and 2011, said after the match. "Obviously to open the tournament and play the first match is never easy, but I really enjoyed it.
"I really tried to focus on what I had to do and I did serve well - I was placing the ball really well around the court - and I was really happy with that. It's tough to play on a new court so I'm really happy to win the match."
"It definitely wasn't good for me - I didn't play my best tennis - and Ana was playing very well, with lots of strong, deep shots that made it hard for me to get into the points," Pironkova said.
"I was also a bit nervous as it was my first match in front of the home crowd. I'm a bit disappointed but I hope the next match will be better for me."