The 2007 National League Division Series (NLDS), the first round of the National League side in Major League Baseball’s 2007 postseason, 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 lose to the American League champion Boston Red Sox in the 2007 World Series.

Arizona won the series, 3–0.

Colorado won the series, 3–0.

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. 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 a sacrifice fly by Conor Jackson. Webb pitched seven innings, Brandon Lyon pitched the eighth, and José Valverde threw a hitless ninth inning to save the game for Arizona.

The Cubs struck first in Game 2 when Matt Murton singled to lead off the second off Doug Davis before Geovany Soto's home run put them up 2–0, but starter Ted Lilly in the bottom of the inning allowed a leadoff single to Chris Snyder, then walked Justin Upton before Chris Young's three-run home run two outs later put them up 3–2. Stephen Drew then singled and scored on Eric Byrnes's triple to make it 4–2 Arizona. In the fourth, Lilly allowed a leadoff single to Augie Ojeda, then walked Young one out later before Drew's triple made it 6–2 Arizona and knocked him out of the game. Kevin Hart walked two with one out next inning before being relieved by Scott Eyre, who allowed an RBI single to Ojeda that put Upton at third. Michael Wuertz relieved Eyre and Davis's fielder choice scored another run for Arizona. In the seventh, Davis walked two with two outs before being relieved by Juan Cruz, who allowed a two-run double to pinch hitter Daryle Ward that made it 8–4 Arizona. However, neither team would score for the rest of the game, so the Diamondbacks went up 2–0 in the series heading to Chicago.

Chris Young's home run on the first pitch of the game off Rich Hill gave Arizona a quick 1–0 lead. Stephen Drew then doubled to right field and after two strikeouts and a walk, scored on Justin Upton's single. Hill would leave the game in the fourth after allowing a lead-off walk and single. Michael Wuertz in relief walked Young to load the bases, then struck out Drew before Eric Byrnes hit into a forceout at second that scored Miguel Montero. The Cubs cut Arizona's lead to 3–1 in the bottom of the inning off Liván Hernández when Mark DeRosa hit a leadoff single, moved to third on Jacque Jones's double, and scored on Jason Kendall's groundout. However, Hernandez would only allow three other hits in six innings. Solo home runs by Byrnes in the sixth off Carlos Marmol and Drew in the ninth off Kerry Wood capped the scoring as the Diamondbacks' 5–1 win completed a sweep of the Cubs, who hit into four double plays.