Ali's marathon 609-minute knock of 272 not out frustrated a hapless West Indies bowling attack as Pakistan piled on the runs on a flat Dubai stadium pitch after they resumed the day on 279-1.
Skipper Misbah-ul-Haq, 10 not out at the break, will look for quick runs to put pressure on the West Indian batsmen as they seek to take a 1-0 lead in the three-match series.
Ali has stolen the spotlight in just the second ever day-night Test, played with a pink ball, surpassing his previous best of 226 against Bangladesh in Dhaka last year.
He added 215 for the first wicket with opener Sami Aslam (90) on the first day and then had two further big partnerships, putting on 147 with Asad Shafiq (67) and another 165 for the third wicket with debutant Babar Azam, who made 69.
Also Read
Azam, given his first Test chance after scoring three hundreds in as many one-day matches in Pakistan's 3-0 rout of the West Indies, batted with authority.
Earlier Ali was given another lifeline when Jermaine Blackwood dropped a regulation catch off spinner Roston Chase in the slips with the Pakistani opener on 190.
Resuming at 279-1, Pakistan lost one wicket in the first session when Shafiq gave a return catch to Bishoo.
Ali continued from where he left off after resuming on 146, reaching his 150 with a single and then hitting a six and a boundary off Chase to send Pakistan past 350.
Shafiq then reached his 15th Test half-century with a well-timed four off Bishoo before missing out on a big score when he mistimed a straight drive.
This three-match series will continue in Abu Dhabi (October 21-25) and Sharjah (October 30-November 3).
Disclaimer: No Business Standard Journalist was involved in creation of this content