Phillies ace Roy Halladay took a 3-1 lead into the seventh, but the Colorado native wound up with a no-decision after Brad Hawpe's tying, two-run triple.
Olivo sent Chad Durbin's first pitch far over the left-field wall, then flipped his bat in celebration. Olivo began the game in a 2-for-28 slump.
Joe Beimel (1-0) threw 1 1-3 scoreless innings. Durbin (0-1) took the loss on a cold, damp and windy day that followed an overnight snowfall.
Before the game, the Phillies insisted Wednesday they weren't trying to steal signs when bullpen coach Mick Billmeyer was caught on camera peering through binoculars from the bullpen bench at Coors Field earlier this week.
Manager Charlie Manuel told The Associated Press that Billmeyer simply was watching Philadelphia catcher Carlos Ruiz set up defensively. Whatever, Major League Baseball officials looked at the tape and told the Phillies to knock it off.
Olivo also singled three times and doubled for his second career five-hit game.
Halladay surrendered three runs, two of them earned, on 10 hits in 6 1-3 innings. He made his first start in Colorado since high school, pitching in a game with weather similar to what he had to deal with as a prep prodigy at Arvada West in the mid-1990s.
J.C. Romero replaced Halladay and Hawpe was stranded when Todd Helton lined out to first and Ian Stewart lined out.
The wintery weather might have had something to do with a double-whammy in the fourth inning when Rockies second baseman Melvin Mora (right leg) and Phillies catcher Carlos Ruiz (right knee) were injured on the same, strange play.
The Rockies inserted Mora into the lineup after deciding they didn't want to take any chances in the cold weather with shortstop Troy Tulowitzki, who strained his right thigh Sunday in Los Angeles.
It was 40 degrees with 75 percent humidity at game time following Tuesday night's rainout and the overnight sleet and snow. With Clint Barmes moving over the shortstop, Mora played second base.
In the fourth, Ruiz hit a groundball to third base, where Stewart stepped on the bag and threw to second base. Mora stretched awkwardly to his right to catch the throw and was unable to pivot and throw to first for a possible triple play.
Ruiz wasn't taking any chances at ignominy and raced down the line, injuring his right knee in the process. He was replaced by pinch-runner Paul Hoover once he reached third base following a double by the next hitter, Wilson Valdez.
The Rockies said Mora strained a gluteal muscle in his right leg and is day-to-day. He was replaced by Eric Young Jr.
Carlos Gonzalez, the Rockies' RBIs leader, returned from his uncle's funeral in Venezuela, and scored from third on Hawpe's shallow fly ball in the first inning that left fielder Raul Ibanez hauled in just several strides beyond the infield dirt.
The Phillies tied it in the third on Jayson Werth's RBI double off Aaron Cook and they took a 3-1 lead in Chase Utley drove in a run with a single and Ibanez hit a sacrifice fly.
Colorado manager Jim Tracy was ejected in the ninth for vehemently arguing first base umpire Corey Blaser's out call on Young's bang-bang play at first.
NOTES: The Phillies sent closer Brad Lidge back to Philadelphia to have his surgically repaired right pitching elbow examined by team doctor Michael Ciccotti. Lidge has said he thinks the stiffness in his elbow is a normal aftereffect of his offseason operation.
