The North China Plain (NCP) is one of the areas with a fast urbanization rate. The proportion of urban areas has increased from 1.78% in 2000 to 6.70% in 2015 in the NCP. Urban expansion induce variations in air pollutants are mainly determined by changes in meteorological conditions and atmospheric physicochemical processes. A persistent severe wintertime particulate pollution episode is simulated using the WRF-Chem model to investigate the impacts of land use/cover change on air quality in the NCP. Sensitivity simulations demonstrated that the urban expansion increases the near-surface temperature by approximately 0.2 °C, and further the development of the planetary boundary layer height by approximately 1.6%, but decreases the relative humidity by 0.4% on average. The near-surface O3 concentrations are increased by 2.2%, but the PM2.5 concentrations are decreased by 2.4% on average in the NCP. The near-surface concentration of NO2, SO2, and CO decrease by 4.5%, 2.2%, and 2.7%, respectively. The decrease in PM2.5 concentrations is approximately 8.9% in urban areas. Although urban expansion increases anthropogenic emissions of air pollutants, it alleviates particulate pollution to some degree, particularly in urban areas.