Valverde, who is a Major League free agent, will not pitch in the Classic because of a personal issue, the Dominican team announced on Friday. Right-hander Lorenzo Barcelo will take Valverde's roster spot.
Two years ago, Valverde enjoyed a flawless regular season for the Tigers, as he converted all 49 of his save opportunities while also earning his second consecutive All-Star Game nod. In 2012, his ERA jumped to 3.78 from 2.24, and he pitched just four times in the postseason, allowing nine runs in 2 2/3 innings, for a 30.38 ERA.
In the Game 1 of the American League Championship Series, Valverde surrendered four runs to the Yankees in the bottom of the ninth to erase a 4-0 Tigers lead. He didn't pitch again until Game 1 of the World Series in San Francisco, when he allowed four hits in one-third of an inning in mop-up duty.
Detroit opted to part ways with the 34-year-old following the season, and Valverde has yet to latch on with a big league team.
The three-time All-Star has tallied 44 or more saves on three occasions, and he owns a 3.11 ERA across 10 seasons.
The Dominican Republic plays its first Classic game on Thursday at 6:30 p.m. ET against Venezuela.
Zack Meisel is a reporter for MLB.com. Follow him on Twitter @zackmeisel. This story was not subject to the approval of Major League Baseball or its clubs.