Arroyo left after five innings of Arizona's 6-3 victory against the Dodgers on Sunday with elbow pain.
The right-hander informed manager Kirk Gibson that he couldn't continue because of pain that had been bothering him since a 110-pitch complete-game victory over Washington on May 13.
''It wasn't that much fun,'' Arroyo said after throwing 78 pitches and allowing a run on five hits. ''I was just getting outs on location and getting comfortable enough in that environment to throw a bunch of slop up there and get guys out. It's been tough for a while. I've won the last three games not knowing if I could really get back out there inning to inning. How I've won all three, I have no idea.''
The 15-year veteran is expecting to get an MRI on Monday.
''When I was throwing 83-85, it was like manageable. But it's slowly sliding downhill. So I may be facing the inevitable for the first time in two decades,'' Arroyo said. ''I can't keep going out there pitching like I did today many more times. It's just getting to the point where there's too much pain, and it's too difficult to get hitters out with that velocity time and time again.''
Goldschmidt hit his 15th home run in the first inning against Josh Beckett (4-4) and Montero hit his 10th in the ninth, a two-run shot off Chris Perez.
For the second time in two games, Montero threw out Puig trying to steal second base in the first inning with Gonzalez at bat. Puig has been caught seven times on 14 steal attempts. Montero entered this series having thrown out only six of 39 runners.
Beckett was charged with four runs - three earned - and five hits through seven innings with six strikeouts and no walks.
Some absentmindedness by the Dodgers helped the Diamondbacks during a two-run seventh inning that increased the lead to 4-1.
Montero ended up with one-out infield single after second baseman Dee Gordon fielded his routine grounder and had neither first baseman Adrian Gonzalez nor Beckett covered the bag.
''I didn't see it off the bat - and then when I saw it, I thought it was going to be between me and Dee. So I went to it,'' said Gonzalez, a three-time Gold Glove winner.
Aaron Hill followed with a single to left field and continued to second as Matt Kemp tried to throw out Montero at third. Gordon then charged Martin Prado's slow grounder with the infield playing in - and ran past the ball as it skidded into short-right-center. Both runners scored and Prado was credited with one RBI.
An error by Arizona shortstop Didi Gregorius on Jamie Romak's leadoff grounder in the seventh gave the Dodgers some life. Lefty Oliver Perez, who came in with a scoreless streak of 11 innings over his previous 13 appearances, walked Drew Butera before pinch-hitter Justin Turner doubled.
Butera was hoping to score behind Romak, then slammed on the breaks after he was held up by coach Lorenzo Bundy. But Gregorius took the relay from Ross and threw to Prado for the tag on Butera.
''When the ball was hit, I was thinking home, but I think I was just a little too aggressive,'' Butera said.
Perez then hit Gordon with an 0-2 pitch, but the D-backs escaped the inning still clinging to a 4-2 lead as Evan Marshall struck out Hanley Ramirez and retired Puig on a tapper back to the mound.
Brad Ziegler escaped the Dodgers' eighth unscathed after retiring Romak on a double-play grounder with runners at the corners.
The Dodgers tied it in the second when Gonzalez drew a leadoff walk and scored on Romak's groundout. The Diamondbacks regained the lead in the fifth when David Peralta doubled with two out, stole third and sprinted home on Beckett's first wild pitch of the season.
NOTES: Ramirez added an RBI double in the ninth for Los Angeles. ... Sixteen of Goldschmidt's 79 big league homers have come in the first inning, more than he's hit in any other frame. Goldschmidt has 13 homers, 44 RBIs and a .321 average against Dodgers pitching. The home run and RBI totals are his best against any club. ... The Dodgers have only six home runs in 417 at-bats and 482 total plate appearances over their last 13 games. Gonzalez has gone 23 games without one and Puig is in a 16-game home run drought.