Starc removed both of Pakistan's openers - Saim Ayub and Abdullah Shafique - to set the tone for Australia as they restricted the tourists to 203 at the MCG on Monday in the first of three ODIs.
The left-armer - who has the fourth most ODI wickets for Australia, only behind Glenn McGrath, Lee and Shane Warne - began the international summer in ominous form.
Starc - who had a brief period off the field to deal with cramp - nailed his line and length to finish with 3-33 after dismissing Pakistan Shaheen Shah Afridi (24) in his 10th over.
Starc's 100th wicket in Australia came in his 54th match, going one better than Lee's 55.
Australia used eight bowlers after Pat Cummins - playing his first ODI since the stunning 2023 World Cup final triumph - won the toss and elected to bowl first.
Legspinner Adam Zampa (2-64) was the only other bowler to take multiple wickets, but went for 18 runs in his 10th over after being hit around the MCG by Naseem Shah.
The Pakistani quick entered the match with just 31 career ODI runs, but smashed 40 during an explosive innings that included four sixes.
Pakistan landed in Australia amid off-field turmoil after respected white-ball coach Gary Kirsten quit his position without actually taking charge in an ODI.
In their first ODI since last year's World Cup, Pakistan struggled to gain any momentum and batted more like a 50-over match in the 1990s.
Babar Azam (37) and new Pakistan white-ball captain Mohammad Rizwan (44) attempted to push towards a competitive total but could never lift the run-rate high enough.Â
Australia's World Cup heroes Travis Head and Mitch Marsh are on paternity leave and will sit out all three games.
Their absence gives young blaster Jake Fraser-McGurk and Matt Short an opportunity at the top of the order and a chance to impress in front of their home crowd.
With David Warner retired, Short and Fraser-McGurk are vying to lock down a spot as Head's opening partner ahead of next year's Champions Trophy in Pakistan.
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