Information on the spatiotemporal variations in the composition and sources of organic aerosols (OA) is needed to identify regional influences and to establish effective control measures. Here, 23-h PM2.5 samples were collected in five central cities of the Yangtze River Delta in eastern China, including Nanjing, Suzhou, Wuxi, Changzhou, and Zhenjiang, every three days from 2020/09/01 to 2021/02/28. Each sample was analyzed for water-soluble inorganic ions, organic carbon (OC), elemental carbon (EC), and organic molecular markers (OMMs). Generally, the major components of PM2.5, including NH4+, SO42−, NO3−, OC, and EC, exhibited similar temporal patterns across the five cities. In all OMM groups, the concentrations of PAHs, oxygenated PAHs, and secondary products of isoprene showed strong correlations (r = 0.79 ± 0.050–0.93 ± 0.028) and low coefficient of divergence (COD = 0.22 ± 0.024–0.30 ± 0.033) between sampling sites, indicating a homogeneous spatial distribution of industrial emissions and biogenic secondary OA in autumn and winter. Other OMMs showed wider r (e.g., steranes and hopanes, 0.20–0.80) and COD (0.26–0.69) ranges for all site pairs, probably due to the influence of local emissions. Based on the source apportionment results using Positive matrix factorization, the biomass burning factor dominated the contribution to OC and EC in winter and showed strong correlations (r = 0.84 ± 0.063) between the sampling sites, indicating regional transport of emissions from biomass burning and fossil fuel combustion in the heating season. Traffic-related factors had the greatest spatial heterogeneity (r = 0.27 ± 0.19–0.51 ± 0.16) and contributed significantly to OC at their maximum levels.
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