Ground-received solar radiation is affected by several meteorological and air pollution factors. Previous studies have mainly focused on the effects of meteorological factors on solar radiation, but research on the influence of air pollutants is limited. Therefore, this study aimed to analyse the effects of air pollution characteristics on solar radiation. Meteorological data, air quality index (AQI) data, and data on the concentrations of six air pollutants (O3, CO, SO2, PM10, PM2.5, and NO2) in nine cities in China were considered for analysis. A city model (model-C) based on the data of each city and a unified model (model-U) based on national data were established, and the key pollutants under these conditions were identified. Correlation analysis was performed between each pollutant and the daily global solar radiation. The correlation between O3 and daily global solar radiation was the highest (r = 0.575), while that between SO2 and daily global solar radiation was the lowest. Further, AQI and solar radiation were negatively correlated, while some pollution components (e.g., O3) were positively correlated with the daily global solar radiation. Different key pollutants affected the solar radiation in each city. In Shenyang and Guangzhou, the driving effect of particles on the daily global solar radiation was stronger than that of pollutants. However, there were no key pollutants that affect solar radiation in Shanghai. Furthermore, the prediction performance of model-U was not as good as that of model-C. The model-U showed a good performance for Urumqi (R2 = 0.803), while the difference between the two models was not particularly significant in other areas. This study provides significant insights to improve the accuracy of regional solar radiation prediction and fill the gap regarding the absence of long-term solar radiation monitoring data in some areas.