Despite enhancements in pollution control measures in southwestern China, detailed assessments of PM_2.5 dynamics following the implementation of the Clean Air Action remain limited. This study explores the PM_2.5 concentrations and their chemical compositions during the winter haze period of 2017 across four major urban centers—Chengdu, Chongqing, Guiyang, and Kunming. Significant variability in mean PM_2.5 concentrations was observed: Chengdu (71.8 μg m⁻³) and Chongqing (53.3 μg m⁻³) recorded the highest levels, substantially exceeding national air quality standards, while Guiyang and Kunming reported lower concentrations, suggestive of comparatively milder pollution. The analysis revealed that sulfate, nitrate, and ammonium (collectively referred to as SNA) constituted a substantial portion of the PM_2.5 mass—47.2% in Chengdu, 62.2% in Chongqing, 59.9% in Guiyang, and 32.0% in Kunming—highlighting the critical role of secondary aerosol formation. The ratio of NO₃⁻/SO₄²⁻ and nitrogen oxidation ratio to sulfur oxidation ratio (NOR/SOR) indicate a significant transformation of NO₂ under conditions of heavy pollution, with nitrate formation playing an increasingly central role in the haze dynamics, particularly in Chengdu and Chongqing. Utilizing PMF for source apportionment, in Chengdu, vehicle emissions were the predominant contributor, accounting for 33.1%. Chongqing showed a similar profile, with secondary aerosols constituting 36%, followed closely by vehicle emissions. In contrast, Guiyang’s PM_2.5 burden was heavily influenced by coal combustion, which contributed 46.3%, reflecting the city’s strong industrial base. Kunming presented a more balanced source distribution. Back trajectory analysis further confirmed the regional transport of pollutants, illustrating the complex interplay between local and distant sources. These insights underscore the need for tailored, region-specific air quality management strategies in southwestern China, thereby enhancing our understanding of the multifaceted sources and dynamics of PM_2.5 pollution amidst ongoing urban and industrial development.