The 29-year-old Higuain opened after 23 minutes in front of a capacity 80 000 crowd at Milan's San Siro Stadium and grabbed a second on 63 minutes for the six-time reigning champions.
It put Juventus provisionally top with 28 points from 11 games just ahead of Napoli on goal difference.
Napoli can reclaim top spot at Sassuolo on Sunday as can Inter Milan who are just two points behind the leaders before visiting Verona on Monday.
"Playing at the San Siro is never easy and Milan are historic rivals. In these fixtures, form is wiped out," said coach Massimiliano Allegri.
"It sets us up nicely for the Champions League on Tuesday."
For Higuain the century of goals in Italy – after achieving the same in Spain – was revenge for his disallowed effort during the week.
"When they disallowed the goal against SPAL, we said it was my destiny to score the 100th at San Siro! Now it's 101, not bad," said the Argentine.
Milan were playing without captain Leonardo Bonucci who was completing his two-match ban against his former club.
But after early pressure from the hosts, Juventus got into their stride with Paulo Dybala weaving his way through for Higuain to blast in his 100th league goal.
Milan's summer signing Nikola Kalinic got the best chance just before the break but Gianluigi Buffon dived to clear and his effort bounced off the crossbar.
Higuain's second again came following excellent teamwork with Ghanian Kwadwo Asamoah crossing for Dybala who let the ball pass between his legs for Higuain to trick Ricardo Rodriguez and rifle past Gianluigi Donnarumma for his sixth league goal of the season.
"Milan perhaps started stronger, but we're a great team and when we play like that it's difficult to beat us," said Higuain.
"The coach said games never end at San Siro and that is absolutely true. We stayed focussed for the full 90 minutes and made only one mistake, when they hit the bar."
MILAN MILLIONS NOT ENOUGH
However, the future looks increasingly bleak for Milan coach Vincenzo Montella whose side are eighth, 12 points behind the leaders, and far below their objective of Champions League football next season.
"We went close to the goal several times, but there are few Higuains out there and not everybody has someone like him," complained Montella who had looked to have stopped the rot with a midweek win at Chievo.
Despite the club's new Chinese owners investing 200 million euros ($232 million) during the summer transfer market the club are sorely lacking not just a big striker but in all areas.
The former European giants have been beaten five times in 11 games without taking a point from a big team with losses to Inter, Roma, Juventus, Lazio and Sampdoria.
Montella hinted that Milan had wanted to sign a top striker this summer, but were hampered by lack of elite European football.
"The match was decided by a top player who created two goals out of nothing," he said.
"Top players worth 100 million euros won't come without the Champions League."
In Saturday's second game, AS Roma took all three points at Bologna thanks to a Stephan El Shaarawy volley, to stay fifth.
It was a family affair as Roma coach Eusebio Di Francesco's son Federico plays as a winger for Bologna.
But it was El Shaarawy who broke through after 33 minutes off an Alessandro Florenz corner.
Juventus travel to Sporting Lisbon in Champions League this week with Roma hosting Chelsea.
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