At stumps, the home side were 381 for eight in reply to the visitors' first innings total of 175, a huge lead of 206.
They will be pushing to complete another comprehensive victory with two days to spare -- as achieved the previous week in Barbados -- to sweep the brief series 2-0 and extend their Test match winning streak to six.
Having earned honorary citizenship of the island in scoring the first Test century at the venue two years ago against India, Chanderpaul strengthened those terms of endearment with Dominicans in a five-hour vigil that was only ended by a controversial catch.
His 108 occupied most of the day after Marlon Samuels fell to the first delivery of the morning.
The other overnight batsman, Gayle, carried on to 101, his 15th Test hundred, an innings embellished with his usual accompaniment of powerfully-driven fours and towering sizes before he became Prosper Utseya's first Test wicket just before lunch.
Utseya also accounted for Chanderpaul after the second new ball failed to provide the desired breakthrough, although the batsman could consider himself very unlucky in not being able to prolong his 28th Test hundred -- his first against Zimbabwe.
Television replays showed that the ball had slipped out of Sean Williams' grasp at cover as he dived to complete the catch.
Playing his 148th Test, the former West Indies captain put on 173 for the fifth wicket with Denesh Ramdin, the wicketkeeper-batsman extending his good run of form since the final Test of the tour of England last June.
But he missed out on a hundred when he was trapped lbw for 86 by Graeme Cremer.
The persevering leg-spinner, who went wicketless and conceded 102 runs in 20 overs in the first Test, also accounted for West Indies skipper Darren Sammy to a catch at long-on, although his final figures of two for 102 off 34 overs represented the sixth consecutive Test innings in which he had conceded over 100 runs.
Utseya finished as the leading wicket-taker on the day, adding a third victim when he bowled Kemar Roach first ball following the dismissal of Chanderpaul.
However, the tourists were left to rue a missed opportunity in the morning to remove the 38-year-old left-hander when he was just on 24, Hamilton Masakadza reacting slowly at leg-slip to a sharp catch off the bowling of the unlucky Cremer.
That, and their failure to make the most of a pitch offering considerable turn and bounce, appears likely to haunt them on day three given the success that local hero Shane Shillingford and part-timer Samuels enjoyed in routing Zimbabwe on the first day.