The 2007 National League Division Series (NLDS), the opening round of the 2007 National League playoffs, began on Wednesday, October 3 and ended on Saturday, October 6, with the champions of the three NL divisions and one wild card team participating in two best-of-five series. They were:

Colorado earned the wild card after winning a one-game playoff with San Diego. Although the division winner with the best record normally plays the wild card team, the Diamondbacks played the Cubs, rather than the wild card Rockies, because the league did not pair teams from the same division against each other in the division series.

Both series represented the first time the opponents had met in the postseason, and the Rockies' victory was their first in any postseason series. The Diamondbacks and the Rockies met in the NL Championship Series, with the Rockies becoming the National League champion and going on to face the American League champion in the 2007 World Series. This was the first time under the expanded playoffs format first used in 1995 that two teams from the National League's Western Division had played against one another in the NLCS.

Arizona won the series, 3–0.

Colorado won the series, 3–0.

Chase Field in Phoenix, Arizona

Eighteen-game winners Carlos Zambrano and Brandon Webb matched each other pitch for pitch in the opening game of the series. The Diamondbacks struck first on Stephen Drew's fourth-inning home run. The Cubs loaded the bases in the sixth on two walks and a hit with two outs, but only scored once on Ryan Theriot's RBI single that tied the game. Unfortunately for Chicago, that would be all their offense as Carlos Mármol would take the loss in relief of Zambrano, allowing a lead off home run to Mark Reynolds in the seventh, then one out later walking Chris Snyder, who moved to third on Augie Ojeda's double and scored on and a sacrifice fly to Conor Jackson. José Valverde threw a hitless ninth inning to save the game for Arizona.

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