Olivia Nelson-Ododa added 16 points and 11 rebounds for UConn (4-0, 3-0 Big East), which was playing for the fourth time in eight days. Freshman Paige Bueckers finished with 19 points and nine assists.
Tennessee transfer Evina Westbrook chipped in with 15 points, Aubrey Griffin had 13 and Aaliyah Edwards added 11.
Nia Clark had 11 points to lead Xavier (3-2, 0-1), which was playing its conference opener.
UConn scored the game’s first 19 points and the Musketeers never threatened to get back into the game, committing 14 first-quarter turnovers.
Williams scored eight points during an 18-0 run later in the quarter and the Huskies led 38-7 after 10 minutes. She had 17 of her points in the first half, Nelson-Ododa added 14 and the Huskies led 60-27 at halftime, making 24 of their 32 shots from the floor (75%).
Xavier scored 17 points in the third quarter, but by then UConn had doubled the Musketeers point total and led 88-44 going into the fourth.
Nelson-Ododa, who hit all nine of her shots in a win over Creighton on Thursday, made her first five on Saturday. She finished 7 of 10 from the floor.
UConn: The Huskies had made just 14 3-point baskets during their first three games and came into the game shooting just 29% from behind the arc. The Huskies made six of their 10 first half 3-pointers and finished with 10 3-pointers on 18 attempts.
Xavier: The Musketeers haven't beaten a top-25 team since taking down then-No. 18 Kansas by five points in November, 2009. Xavier is 11-46 against ranked opponents all-time.
Xavier: The Musketeers are scheduled to host Marquette on Tuesday.
UConn: The Huskies are scheduled to travel to Pennsylvania to face Villanova on Tuesday.