In the present work, a method was developed for determining lead, zinc, copper, cadmium, znd chromium in PM2.5 by inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis with microwave digestion and glass fibre filter collection of samples. The microwave digestion systems were investigated and the experimental conditions were optimized. The results show that (1) HNO3-H2O2 digestion system is more stable and complete than HNO3-HCl and HNO3-H2SO4 digestion systems; (2) The most sensitive emission wave length of lead, zinc, copper, cadmium, and chromium are 220.353, 213.857, 327.393, 228.802, and 267.716 nm, respectively; (3) The highest signal-to-noise ratios were observed under the conditions: RF power of 1 300 W, peristaltic pump flow rate of 1.5 mL·min-1, cooling gas flow rate of 15 L·min-1, and carrier gas flow rate of 0.8 L·min-1. In addition, the detection limit for these elements ranged between 2.02×10-3 and 8.20×10-3 μg·mL-1, the relative standard deviations (RSD, n=6) for the samples were in the range of 1.86%～2.82%, and the recovery for the elements determined was from 91.6% to 103.7%. The proposed method was used for determination of the above five elements in atmospheric fine particulate matter at Wanzhou Monitoring Site of Chongqing Institute of Green and Intelligent Technology. The results revealed that the atmospheric fine particulate matter at this monitoring site was not polluted by cadmium and chromium, lead was at the level of potential contamination, while zinc and copper were at the level of slight pollution.