MLB.com's No. 9 preseason prospect went 2-for-4 with a homer and three RBIs, leading Triple-A Scranton/Wilkes-Barre to an 8-3 win over Syracuse.
Montero did not start in either of the Yankees' previous two games because of an eye infection. The ailment also caused him to miss several games earlier in the week.
After popping out to catcher in his first at-bat Monday, Montero homered on the first pitch he saw from Major League veteran Tom Gorzelanny in the third. The longball knocked in three runs and broke an 0-for-14 streak for Montero dating back to June 3.
The 21-year-old catcher later singled in the seventh and walked in the ninth. He also made an impact in the field, tagging out the Chiefs' Chris McConnell at home to end the seventh when the shortstop attempted to score from second on Matt Antonelli's single.
Overall, Montero is hitting .293 with five home runs this year. Signed by the Yankees as a free agent in 2006, he batted .289 with 21 homers in 123 games at Triple-A last season.
Cory Wade (3-1) earned the win in his debut for Scranton/Wilkes-Barre by pitching 1 2/3 scoreless innings of relief. The 28-year-old right-hander was released by the Rays over the weekend and signed by the Yankees on Monday.
David Phelps was originally slated to start the game for Scranton/Wilkes-Barre but was scratched late. With Bartolo Colon going on the disabled list Sunday, Phelps is a candidate to start in his stead for the big league club Thursday.
"We will see -- just preserving all options," Yankees GM Brian Cashman told Newsday.
George Kontos took Phelps' place for the Baby Bombers, tossing four innings of one-hit, one-run ball.
In the first game of his rehab assignment, Gorzelanny (0-1) was tagged with the loss after giving up four runs on five hits over four innings. He was placed on the DL on May 24 with left elbow inflammation.