Much of the pre-match discussion had centered on Italy's striking options, with coach Antonio Conte calling up Graziano Pelle at Mario Balotelli's expense for the Euro 2016 qualifying Group H clash at the Stadio Renzo Barbera in Palermo.
However, Chiellini stole the show for both positive and negative reasons, having initially opened the scoring late in the first half when he headed in Andrea Pirlo's corner.
Chiellini made an altogether more unwanted contribution when he mistakenly bundled the ball into his own net from a corner with 13 minutes remaining - the first goal conceded by Italy under Conte's tenure.
However, the 30-year-old made amends with what proved to be the winner as he powered a header past Kamran Agayev with eight minutes left on the clock.
It capped off an eventful evening, both for Chiellini and Italy, but maintained Conte's winning start to life with the national side.
Keeping the ball well, Italy began brightly as Simone Zaza failed to connect with Mattia De Sciglio's cross from the left just four minutes in.
Claudio Marchisio was next to go close, as Ciro Immobile beat Rashad Sadygov and cut the ball back - only for the Juventus man to scoop his effort over the crossbar.
The hosts' dominance in possession continued but Conte's side had to wait until the 26th minute for their next sight on goal when an unmarked Leonardo Bonucci stooped to head at goal.
His effort was comfortably saved by Agayev, with Andrea Ranocchia next to go close with a headed effort from Pirlo's cross.
However, Italy's aerial threat eventually paid off two minutes before the break when Chiellini nodded home Pirlo's corner, after Agayev had failed to collect the cross.
Zaza's audacious acrobatic effort early in the second half almost doubled Italy's advantage and the Sassuolo man was among the action soon after when he put Alessandro Florenzi's cross wide.
Chiellini's own goal, under pressure from Rauf Aliyev, looked set to deny Italy the three points their dominance warranted.
However, the Juve man's relief was evident when he got himself and Italy out of trouble late on with a header from substitute Sebastian Giovinco's corner to maintain Italy's 100 per cent start to their qualifying campaign.
