We undertook this study to investigate whether there is an association between atmospheric fine particles (PM2.5) levels and inpatient admissions for chronic obstructive pulmonary disease (COPD) in Taipei, Taiwan. Data on inpatient admissions for COPD and ambient on air pollution levels in Taipei were obtained for years 2006 to 2010. We estimated the relative risk of inpatient admissions for COPD using a case-crossover design with the following control variables: weather measures, day of the week, seasonality, and long-term time trends. For the single-pollutant model (not controlling for other atmospheric pollutants), COPD admissions were significantly and positively associated with higher PM2.5 levels during both warm days (>23 °C) and cool days (<23 °C), with an interquartile range increase of 12% (95% CI = 8–16%) and 3% (95% CI = 0–7%) in COPD admissions, respectively. In the two-pollutant models, PM2.5 remained significant even controlling for SO2 or O3 on both warm and cool days. Taken as a whole, our study demonstrates that higher levels of PM2.5 may increase the risk of inpatient admissions for COPD.