The extent of PM2.5 pollution has reduced in traditional polluted regions such as the North China Plain (NCP), Yangtze River Delta (YRD), Sichuan Basin (SB), and Pearl River Delta (PRD) over China in recent years. Despite this, the Twain-Hu Basin (THB), which covers the lower flatlands in Hubei and Hunan provinces in central China, was found to be a high PM2.5 pollution region, with annual mean PM2.5 concentrations of 41–63 μg·m−3, which is larger than the values in YRD, SB, and PRD during 2014–2019, and high aerosol optical depth values (>0.8) averaged over 2000–2019 from the MODIS products. Heavy pollution events (HPEs) are frequently observed in the THB, with HPE-averaged concentrations of PM2.5 reaching up to 183–191 μg·m−3, which exceeds their counterparts in YRD, SB, and PRD for 2014–2019, highlighting the THB as a center of heavy PM2.5 pollution in central China. During 2014–2019, approximately 65.2% of the total regional HPEs over the THB were triggered by the regional transport of PM2.5 over Central and Eastern China (CEC). This occurred in view of the co-existing HPEs in the NCP and the THB, with a lag of almost two days in the THB-PM2.5 peak, which is governed by the strong northerlies of the East Asian monsoon (EAM) over CEC. Such PM2.5 transport from upstream source regions in CEC contributes 60.3% of the surface PM2.5 pollution over the THB receptor region. Hence, a key PM2.5 receptor of the THB in regional pollutant transport alters the distribution patterns of PM2.5 pollution over China, which is attributable to the climate change of EAMs. This study indicates a complex relationship between sources and receptors of atmospheric aerosols for air quality applications.