Aaron Rodgers threw for 219 yards and a touchdown for Green Bay, which evened its record at 1-1 following an opening loss to San Francisco, but it was the Packers' defense that stole the spotlight while making things difficult for Chicago quarterback Jay Cutler.
Cutler was sacked seven times with Matthews being credited for 3.5 of them from his linebacker position. Williams, a 6-year veteran cornerback, had two of Green Bay's four interceptions.
Green Bay took a 13-0 halftime lead on field goals of 48 and 35 yards by Mason Crosby and a 27-yard scoring throw on a fake punt by Tim Masthay to Tom Crabtree.
After the teams traded field goals in the second half, Rodgers put the game away by hitting Donald Driver with a 26-yard scoring pass with 11:17 to play.
Cutler's 21-yard throw to Kellen Davis with 6:49 remaining accounted for Chicago's only touchdown as the Bears fell to 1-1.
Green Bay has defeated Chicago in seven of their last eight meetings, including a 21-14 victory in the 2010 NFC title game on the Packers' way to a Super Bowl crown.
Rodgers hit 22-of-32 passes with an interception. Cutler was a mere 11-of-27 for 126 yards.
Chicago was held to 168 total yards and averaged only 2.9 yards per play.