Based on environmental monitoring data, meteorological data and the results of numerical simulation, a typical air pollution process in Nanjing, from 26th May to 1st June, 2014 was deeply analyzed combining aerosol extinction coefficient derived from LiDAR system. Experimental results showed that the entire pollution process was affected by both local pollution and exogenous inputs including dust and smoke. Meteorological factors played a significant role in the generation and elimination of pollutants. Low pressure and temperature inversion also hindered the diffusion of pollutants, while strong rainfall terminated the pollution process. During the pollution, the height of atmospheric boundary layer was lower than normal situation and changed little during the pollution period, which provided a poor diffusion condition for pollutants. LiDAR could accurately detect aerosol vertical structure which was able to capture the temporal and spatial variation of pollutant distributions. Therefore, LiDAR can be of great significance for the atmospheric pollution monitoring.