Pitching in the playoffs for the first time in his 11-year career, Wolf lasted 3 2-3 innings against Carpenter, who came in with a career 5-1 record and 2.53 ERA in the postseason.
Matt Kemp hit a two-run homer off Carpenter in the first inning, giving the NL West champions the lead for good.
The teams set a division series record by stranding a combined 30 runners. The Dodgers left 16, including 12 in scoring position.
Offense was at a premium for both teams' sluggers. The Dodgers' Manny Ramirez went 1 for 4 with double and a walk, while Albert Pujols was 0 for 3 with two intentional walks for the NL Central champion Cardinals.
Wolf was the Dodgers' most consistent starter this season, with a 2.98 ERA in the second half and just one loss since Aug. 1 for his hometown team. Against the Cardinals, the left-hander from the San Fernando Valley allowed two runs and six hits, walked five and struck out two.
Jeff Weaver, who relieved Wolf, got the victory, allowing one hit in 1 1-3 innings and striking out one. Jonathan Broxton pitched 1 1-3 innings earn the save.
Game 2 is Thursday at Dodger Stadium, with Clayton Kershaw, another playoff rookie, starting for Los Angeles against 19-game winner Adam Wainwright. Only once this season when Carpenter and Wainwright started back-to-back did St. Louis lose both games.
Carpenter, who was the NL's ERA leader while going 17-4 and went 2-0 against the Dodgers this season, gave up four runs and nine hits in five innings. The right-hander walked four and struck out three. He escaped a bases-loaded jam in the fourth when Casey Blake lined out to right.
Carpenter went 12-1 after the All-Star break, losing once since June 30. He allowed four runs just twice in that span.
The Cardinals reduced their deficit to 5-3 in the ninth, getting a two-out RBI double from Mark DeRosa. Broxton then struck out Rick Ankiel to end it.
Skip Schumaker's RBI double in the fourth cut the Dodgers' lead to 3-2. After Wolf hit Matt Holliday with a pitch to load the bases, Weaver came in.
Ryan Ludwick pulled a drive into the right-field corner that barely landed foul. Ludwick then hit a bouncer back to Weaver, who threw to first to end the inning.
Yadier Molina came within a few feet of hitting a three-run homer in the St. Louis third, forcing Andre Ethier to make a running catch on the warning track in right field.
The Dodgers made it 3-1 in the bottom of the third when Ethier was hit by a pitch, moved up on a walk to Ramirez and took third on James Loney's flyout.
Third baseman Mark DeRosa made a diving, backhanded stop of Blake's infield hit down the line, but his throw to second sailed into right field. In the second, DeRosa banged his right hand into Loney while scrambling back to first base on a lineout.
Wolf let St. Louis load the bases with no outs in the first. But he allowed just one run on Ryan Ludwick's bloop single to center between Kemp and Ronnie Belliard, and then Kemp put Los Angeles ahead.
The Dodgers needed a mere three pitches to take a 2-1 lead. Rafael Furcal led off with a single and Kemp sent Carpenter's third pitch over the wall in right center for his first postseason homer. Carpenter allowed a pair of two-out singles before striking out Belliard.
Carpenter escaped a bases-loaded situation in the fourth when he got Blake to line out to right field.
Furcal extended Los Angeles' lead to 4-2 in the fifth with a sacrifice fly.
Los Angeles loaded the bases again in the sixth, and Kyle McClellan hit Russell Martin to force in Ethier with the Dodgers' fifth run. Pinch-hitter Jim Thome struck out with the bases loaded, ending the inning.
NOTES: The Cadinals fell to 6-2 in division series openers while returning to the playoffs for the first time since winning the 2006 World Series. ... They won five of seven games against the Dodgers this season and outscored them 31-19. ... Dodgers manager Joe Torre began his 14th consecutive playoff run, tying a record for managers set by Atlanta's Bobby Cox (1991-2005). ... Tommy Davis and Maury Wills, who starred on the Dodgers' 1959 World Series championship team, tossed out ceremonial first pitches to "catchers" Juan Pierre and Orlando Hudson. ... Former Dodger closer Eric Gagne blew a kiss to the cheering fans when he was shown in the crowd.