The Integrated Process Rate (IPR) analysis embedded in CAMx model was used to quantify contributions from different atmospheric processes to the formations and accumulations of ambient PM2.5 and the secondary inorganic aerosol (SIA) during two typical particulate pollution episodes in different seasons in the Pearl River Delta (PRD) region. Process analysis results indicated that primary fine particle emissions were the major sources of high ambient PM2.5 in urban areas with intensive anthropogenic activities. Aerosol process and advection transport were another two major processes contributing to the increasing PM2.5 and SIA over the PRD region. Regarding formation of SIA species, elevations of nitrate and ammonium at Guangzhou (urban), Heshan (rural) and Panyu (suburban) sites were largely associated with aerosol process, while those at Huizhou (urban) site were dominated by advection process, but elevated sulfate concentrations at these four sites were all dominated by advection process. The difference can be attributed to spatial variations of SO2, NOx and NH3 emissions, site locations and meteorological conditions. Advection, aerosol chemistry, deposition and vertical diffusion were important pathways to remove SIA at these four sites. Within the hours with most growing PM2.5 concentrations, aerosol process was the most important contributor to the formation of new SIA throughout the entire planetary boundary layer.