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Surface solar radiation (SSR) can affect climate, the hydrological cycle, plant photosynthesis, and solar power. The values of solar radiation at the surface reflect the influence of human activity on radiative climate and environmental effects, so it is a key parameter in the evaluation of climate change and air pollution due to anthropogenic disturbances. This study presents the characteristics of the SSR variation in Nanjing, China, from March 2016 to June 2017, using a combined set of pyranometer and pyrheliometer observations. The SSR seasonal variation and statistical properties are investigated and characterized under different air pollution levels and visibilities. We discuss seasonal variations in visibility, air quality index (AQI), particulate matter (PM10 and PM2.5), and their correlations with SSR. The scattering of solar radiation by particulate matter varies significantly with particle size. Compared with the particulate matter with aerodynamic diameter between 2.5 mu m and 10 mu m (PM2.5-10), we found that the PM2.5 dominates the variation of scattered radiation due to the differences of single-scattering albedo and phase function. Because of the correlation between PM2.5 and SSR, it is an effective and direct method to estimate PM2.5 by the value of SSR, or vice versa to obtain the SSR by the value of PM2.5. Under clear-sky conditions (clearness index >= 0.5), the visibility is negatively correlated with the diffuse fraction, AQI, PM10, and PM2.5, and their correlation coefficients are -0.50, -0.60, -0.76, and -0.92, respectively. The results indicate the linkage between scattered radiation and air quality through the value of visibility.