Thompson acknowledged before Monday's match that Berrettini had "broken Australian hearts" in the Davis Cup semi-finals earlier this year with his win over Thanasi Kokkinakis.
But Thompson warmed the hearts of the Brisbane fans with his 3-6 6-3 6-4 win at Pat Rafter Arena on Monday.
Matteo Berrettini claimed the first set before Thompson fought back to win. (Jono Searle/AAP PHOTOS)
Berrettini, a 2021 Wimbledon finalist, was slick in the opening set.with his service game on song.
He broke the Australian just once where his low, sliced backhands proved tough to return.
The duo shared service breaks early in the second set before Thompson displayed shrewd tactics.
On break point in the sixth game, the receiving Thompson stayed a long way behind the baseline, a move that appeared to confuse the Italian as he put a shot into the net.
Thompson then served two aces at 30-all to take a 5-2 lead. Two games later he served out for the set to take the match into a decider.
The contest ramped up in quality and intensity in the final set with a suite of longer points. Berrettini served a double fault to give Thompson the break in the fifth game as his crafty positional movements while receiving paid dividends.
"I was just trying to give him a different look on serve. He was serving unbelievable at the start so I thought I would try and throw him off his rhythm," Thompson said.
"He has a huge serve and a huge forehand and trying to pin him in that backhand corner is not as easy as it sounds."
The 30-year-old did not relinquish his grip on the match.
Thompson played a clever tactical game to unsettle Berrettini. (Jono Searle/AAP PHOTOS)
Eighth-seed and world No.26 Thompson beat Rafael Nadal in the previous Brisbane tournament, triggering a stellar year for the 30-year-old which included his first ATP Tour win at the Los Cabos Open.
"(Nadal) is one of my childhood heroes and to take him down on this court in a quarter-final on a Friday night really kick-started my year," Thompson said.
Thompson and Berrettini had not met on court since the 2019 US Open when the Italian triumphed in four sets.
Nick Kyrgios completed a fine day for the locals when he teamed with superstar Novak Djokovic to notch an entertaining 6-4 6-7 (4-7) 10-8 doubles win over Alexander Erler and Andreas Mies.
"That was awesome," Djokovic said after helping Kyrgios return to the tour in style after more than two years out of the game with wrist and knee injuries.
Djokovic was also making a comeback of sorts after skipping the year-ending ATP Finals following a season that included knee surgery and yielded Olympic gold but no tour titles.
The pair will begin their singles campaigns on Tuesday, with Djokovic to face Australian Rinky Hijikata and former Brisbane champion Kyrgios up against big-serving Frenchman Giovanni Mpetshi Perricard.
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