To investigate the impact on urban air pollution by crop residual burning outside Nanjing, aerosol concentration, pollution gas concentration, mass concentration, and water-soluble ion size distribution were observed during one event of November 4-9, 2010. Results show that the size distribution of aerosol concentration is bimodal on pollution days and normal days, with peak values at 60-70 and 200-300 nm, respectively. Aerosol concentration is 104 cm-3. nm-1 on pollution days. The peak value of spectrum distribution of aerosol concentration on pollution days is 1.5-3.3 times higher than that on a normal day. Crop residual burning has a great impact on the concentration of fine particles. Diurnal variation of aerosol concentration is trimodal on pollution days and normal days, with peak values at 03:00, 09:00 and 19:00 local standard time. The first peak is impacted by meteorological elements, while the second and third peaks are due to human activities, such as rush hour traffic. Crop residual burning has the greatest impact on SO2 concentration, followed by NO2, O3 is hardly affected. The impact of crop residual burning on fine particles (< 2.1 μm) is larger than on coarse particles (> 2.1 μm), thus ion concentration in fine particles is higher than that in coarse particles. Crop residual burning leads to similar increase in all ion components, thus it has a small impact on the water-soluble ions order. Crop residual burning has a strong impact on the size distribution of K+, Cl-, Na+, and F- and has a weak impact on the size distributions of NH4+, Ca2+, NO3- and SO42-.