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• Long-term exposure to PM 2.5 are associated with large- and small- airway function. • Organic matter and nitrate show stronger associations with lung function than PM 2.5. • Exposure to PM 2.5 constituents might be more important in impairing lung function. The associations of long-term exposure to various constituents of fine particulate matter (≤2.5 μm in aerodynamic diameter, PM 2.5) air pollution with lung function were not clearly elucidated in developing countries. The aim was to evaluate the associations of long-term exposure to main constituents of PM 2.5 with lung function in China. This is a nationwide, cross-sectional analysis among 50,991 study participants from the China Pulmonary Health study. Multivariable linear regression models were used to obtain differences of forced expiratory volume in 1 s (FEV 1), forced vital capacity (FVC), FEV 1 /FVC, peak expiratory flow (PEF), and forced expiratory flow at 25–75% of exhaled FVC (FEF 25-75%) associated with an interquartile range (IQR) change of PM 2.5 or its constituents. Residential annual PM 2.5 levels varied from 26 μg/m3 to 92 μg/m3 (average: 53 μg/m3). An IQR increase of PM 2.5 concentrations was associated with lower FEV 1 (19.82 mL, 95% CI: 11.30–28.33), FVC (17.45 mL, 95% CI: 7.16–27.74), PEF (86.64 mL/s, 95% CI: 59.77–113.52), and FEF 25-75% (31.93 mL/s, 95% CI: 16.64–47.22). Black carbon, organic matter, ammonium, sulfate, and nitrate were negatively associated with most lung function indicators, with organic matter and nitrate showing consistently larger magnitude of associations than PM 2.5 mass. This large-scale study provides first-hand epidemiological evidence that long-term exposure to ambient PM 2.5 and some constituents, especially organic matter and nitrate, were associated with lower large- and small- airway function. [ABSTRACT FROM AUTHOR]