Numerous machine learning models have been widely used for the spatial prediction of PM_2.5 mass concentrations in the field of remote sensing, but most studies rely on single models, limiting their ability to capture complex nonlinear relationships. Furthermore, traditional Aerosol Optical Depth (AOD) methods suffer from extensive missing values due to algorithmic limitations, hindering daily PM_2.5 mass concentration retrieval. This study first developed a hybrid random forest and extreme gradient boosting model (RF-XGBoost) to overcome single-model accuracy constraints. Subsequently, Top-of-Atmosphere (TOA) reflectance replaced conventional AOD as the hybrid model’s input. Finally, we integrated four-year (2020–2023) TOA reflectance, normalized difference vegetation index (NDVI) data, meteorological data, digital elevation model (DEM) data, and day-of-year data to develop a high-precision hybrid model specifically optimized for Jiangxi Province. The simulation results demonstrated that the hybrid RF-XGBoost model (test-R² = 0.82, RMSE = 7.25 μg/m³, MAE = 4.90 μg/m³) outperformed the single Random Forest Model by 25% and 26% in terms of the root mean square error (RMSE) and mean absolute error (MAE), respectively. The high predictive accuracy of our method confirms its effectiveness in generating reliable PM_2.5 estimates. The resulting four-year dataset also successfully delineated the characteristic seasonal PM_2.5 pattern in the region, with the highest levels in winter and the lowest in summer, alongside a clear decreasing annual trend, signifying gradual atmospheric improvement.