The new-generation FengYun geostationary meteorological satellite has a high spatial and temporal resolution, which is advantageous in environmental assessments and air pollution monitoring. This study researched the ground-level particulate matter concentration estimation, based on satellite-observed radiations. The radiation of ground-level particulate matter is separate from the apparent radiation observed by satellites. The positive correlation between PM2.5 and PM10 is also considered to improve the accuracy of inversion results and the interpretability of the estimation model. Then, PM2.5 and PM10 concentrations were estimated synchronously every 5 min in mainland China based on FY-4A satellite directly observed radiations. The validation results showed that the improved model estimated results were close to the ground site measured results, with a high determination coefficient (R2) (0.89 for PM2.5, and 0.90 for PM10), and a small Root Mean Squared Error (RMSE) (4.69 μg/m3 for PM2.5 concentrations, and 13.77 μg/m3 for PM10 concentrations). The estimation model presented a good performance in PM2.5 and PM10 concentrations during typical haze and dust storm cases, indicating that it is applicable in different weather conditions and regions.