The pair set an Australian opening partnership record with a stand of 284, which was just two runs away from equalling the world record, and was also the second-highest opening ODI stand ever.
Warner hit 179 off 128 deliveries, clinching his 11th consecutive century in ODI matches, while Head hit a knock of 128, which included three sixes and nine boundaries.
In 50 overs, the hosts posted 369-7 - Australia's seventh-highest title in ODI history - leaving Pakistan with a mountain to climb in reply.
Khan hit 79 off 69 balls, while Azam reached a century before he was caught by Head off the bowling of Josh Hazlewood.
Umar Akmal was sent packing four runs short of a half-century, and Pakistan were unable to reach their target as they were bowled out for 312 with five balls remaining.