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Fine particulate matter (PM2.5) is a typical air pollutant and has adverse health effects across the world, especially in the rapidly developing China due to significant air pollution. The PM2.5 pollution varies with time and space, and is dominated by the locations owing to the differences in geographical conditions including topography and meteorology, the land use and the characteristics of urbanization and industrialization, all of which control the pollution formation by influencing the various sources and transport of PM2.5. To characterize these parameters and mechanisms, the 5-year PM2.5 pollution patterns of Jiangsu province in eastern China with high-resolution was investigated. The Kriging interpolation method of geostatistical analysis (GIS) and the HYbrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model were conducted to study the spatial and temporal distribution of air pollution at 110 sites from national air quality monitoring network covering 13 cities. The PM2.5 pollution of the studied region was obvious, although the annual average concentration decreased from previous 72 to recent 50 μg m−3. Evident temporal variations showed high PM2.5 level in winter and low in summer. Spatially, PM2.5 level was higher in northern (inland, heavy industry) than that in eastern (costal, plain) regions. Industrial sources contributed highest to the air pollution. Backward trajectory clustering and potential source contribution factor (PSCF) analysis indicated that the typical monsoon climate played an important role in the aerosol transport. In summer, the air mass in Jiangsu was mainly affected by the updraft from near region, which accounted for about 60% of the total number of trajectories, while in winter, the long-distance transport from the northwest had a significant impact on air pollution.