Ali's unbeaten 146 guided Pakistan to 279-1 at close on the opening day of the first Test -- just the second day-night match in Test cricket's 140-year history -- after Misbah-ul-Haq won the toss and opted to bat on a flat Dubai stadium pitch.
Asad Shafiq was the other not out batsman with 33.
Cricket saw the innovation of day-night Tests with a pink ball for the first time when Australia played New Zealand at Adelaide in November last year, attempting to reverse the trend of dwindling Test crowds.
Australia won the low-scoring affair on the third day by a narrow three-wicket margin, with Australian wicket-keeper Peter Nevill's 66 the top individual score.
Ali bettered that and put his name in the records book with a 366-minute stay at the crease, hitting 14 boundaries, but unlike Adelaide where the attendance was 123,000 over three days, only 500-odd people passed through the gates in Dubai.
Despite the empty stands Ali and Sami Aslam, who fell for 90, started brightly with an imperious 215-run stand for the opening wicket.
Ali drove off-spinner Roston Chase to mid-off for his ninth boundary to complete his 11th Test century -- his second in three matches -- before pumping the air in jubiliation.
Aslam, 20, missed out on a hundred by 10 runs when he swept Chase onto his stumps. He hit nine fours in his 290-minute stay at the crease.
It was a second time unlucky for Aslam who was run out for 82 in the Birmingham Test against England two months ago.
Chase was the lone wicket-taker with 1-63 in 21 overs.
"I got run out at Birmingham and here I fell short again but this is cricket and I am unlucky," said Aslam. "The occasion of 400th Test excited the players so it's befitting that we made a good score."
Earlier Ali and Aslam dominated the bowling in the first two sessions as the opening pair added 91 in the second session after they were 81-0 at tea.
West Indies used up both of their referrals, first against Ali off paceman Jason Holder when the batsman was on 38, and then on Aslam (69) off leg-spinner Devendra Bishoo -- both leg-before appeals.
West Indies' spinners failed to create any problems for Pakistan's openers who flourished as the day progressed.
It couldn't have been a better start for Pakistan in a milestone match marking their 400th Test, as they won a crucial toss and made excellent early progress.
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