Bangladesh, making their debut in the competition, could hardly do anything to stop the left-handed Madhya Pradesh batsman, who came to the crease when the hosts, after electing to bat, were in a bit of trouble at 24 for two.
Ali (122) got fine support from Devendra Bundela, another MP player, who was unbeaten on 83 at stumps and the duo put on 214 for the third wicket to put Central Zone in a commanding position at the Karnail Singh stadium.
At close, skipper JP Yadav on 10 was giving company to Bundela.
There seemed to be no respite to the visitors, who were thumped by an innings by East Zone in their tournament opener, as they were sent on a leatherhunt by Ali and Bundela under a scorching sun.
After the early dismissal of both the openers - Sanjay Bangar for 11 and Amit Pagnis for 12, Ali and Bundela joined forces and occupied the crease for almost the entire day.
Ali's 205-ball innings lasted over four hours during which he hit 20 fours and one six, while his partner played more cautiously for his 238-ball knock that contained 10 boundaries.
Bangladesh, playing the match with three seamers, had a good start as the openers struggled for runs.
The pair put on just 16 runs for the first wicket that came in close to one hour before Pagnis was dismissed, falling leg before to Anwar Hussain to a delivery that kept low.
Bangar had also trouble in negotiating the new ball and he was in fact hit on the left elbow by a rising ball from Talha Jubair for which he had to undergo an x-ray. The test, however, revealed nothing serious.
The opener, though continued with a swollen elbow, did not last long. He was trapped leg before by Jubair soon after.
Bangar's dismissal brought Ali and Bundela together and the duo stiched together a fine partnership much to the frustration of the Mohammed Ashrafful led Bangladeshi side.
Ali fell just five overs before close when he played a tired-looking shot off spinner Alok Kapali to be latched at covers by Abdur Razzaq. But by then, the he had accomplished what was required of him. "The big partnership was a bit frustrating after we got two quick wickets. The flat track also did no good to our cause," a frustrated Bangladesh coach Dave Whatmore said after the day's proceedings.