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.
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.
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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.
It was a second time unlucky for Aslam who was run out for 82 in the Birmingham Test against England two months ago.
West Indies took the second new ball as soon as it was due after 80 overs with Pakistan on 249-1 but failed to get another wicket.
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."
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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