The use of satellite data to estimate PM2.5 is an appropriate approach for long-term, substantial monitoring and assessment. To estimate PM2.5, the majority of the algorithms now in use utilize the top-of-atmosphere (TOA) reflectance or aerosol optical depth (AOD) derived from scalar satellite data. However, there is relatively little research on the retrieval of PM2.5 using multi-angle polarized data. With its directional polarimetric camera (DPC), the Chinese new-generation satellite Gaofen 5B (henceforth referred to as GF-5B) offers a unique opportunity to close this gap in multi-angle polarized observation data. In this research, we utilized TOA data from the DPC payload and applied the gradient boosting machine method to simulate the impact of the observation angle, wavelength, and polarization information on the accuracy of PM2.5 retrieval. We identified the optimal conditions for the effective estimation of PM2.5. The quantitative results indicated that, under these optimal conditions, the PM2.5 concentrations retrieved by GF-5B showed a strong correlation with the ground-based data, achieving an R2 of 0.9272 and an RMSE of 7.38 µg·m−3. By contrast, Himawari-8’s retrieval accuracy under similar data conditions consisted of an R2 of 0.9099 and RMSE of 7.42 µg·m−3, indicating that GF-5B offers higher accuracy. Furthermore, the retrieval results in this study demonstrated an R2 of 0.81 when compared to the CHAP dataset, confirming the feasibility and effectiveness of the use of GF-5B for PM2.5 retrieval and providing support for PM2.5 estimation through multi-angle polarized data.