The quantitative assessment of the spatial and temporal variability and drivers of fine particulate matter (PM2.5) fraction concentrations is important for pollution control and public health preservation in China. In this study, we investigated the spatial temporal variation of PM2.5 chemical component based on the PM2.5 chemical component datasets from 2000 to 2019 and revealed the driving forces of the differences in the spatial distribution using a spatial regression model and a two-step clustering approach. The results show that: the PM2.5 chemical fraction concentrations show a trend of first increasing (2000–2007) and then decreasing (2007–2019). From 2000 to 2019, the change rates of PM2.5, organic matter (OM), black carbon (BC), sulfates (SO2– 4), ammonium(NH + 4), and nitrates ༈NO– 3༉ were − 0.59, − 0.23, − 0.07, − 0.15, − 0.02, and 0.04µg/m3/yr in the entirety of China. The secondary aerosol (i.e., SO2– 4, NO– 3, and NH + 4; SNA) had the highest fraction in PM2.5 concentrations (55.6–68.1% in different provinces), followed by OM and BC. Spatially, North, Central, and East China are the regions with the highest PM2.5 chemical component concentrations in China, meanwhile, they are also the regions with the most significant decrease in PM2.5 chemical fraction concentrations. The regression results show that among all variables, the number of enterprises, disposable income, private car ownership, and the share of secondary industry non-linearly enhance the differences in the spatial distribution of PM2.5 component concentrations. Electricity consumption has the strongest influence on NH + 4 emissions in Northwest China and BC and OM emissions in Northeast China.