Surface reflectance (SR) estimation is the most essential preprocessing step for multi-sensor remote sensing inversion of geophysical parameters. Therefore, accurate and stable atmospheric correction is particularly important, which is the premise and basis of the quantitative application of remote sensing. It can also be used to directly compare different images and sensors. The Landsat-8 Operational Land Imager (OLI) and Sentinel-2 Multi-Spectral Instrument (MSI) surface reflectance products are publicly available and demonstrate high accuracy. However, there is not enough validation using synchronous spectral measurements over China’s land surface. In this study, we utilized Moderate Resolution Imaging Spectroradiometer (MODIS) atmospheric products reconstructed by Categorical Boosting (CatBoost) and 30 m ASTER Global Digital Elevation Model (ASTER GDEM) data to adjust the relevant parameters to optimize the Second Simulation of Satellite Signal in the Solar Spectrum (6S) model. The accuracy of surface reflectance products obtained from the optimized 6S model was compared with that of the original 6S model and the most commonly used Fast Line-of-sight Atmospheric Analysis of Spectral Hypercubes (FLAASH) model. Surface reflectance products were validated and evaluated with synchronous in situ measurements from 16 sites located in five provinces of China: Fujian, Gansu, Jiangxi, Hunan, and Guangdong. Through the indirect and direct validation across two sensors and three methods, it provides evidence that the synchronous measurements have the higher and more reliable validation accuracy. The results of the validation indicated that, for Landsat-8 OLI and Sentinel-2 MSI SR products, the overall root mean square error (RMSE) calculated results of optimized 6S, original 6S and FLAASH across all spectral bands were 0.0295, 0.0378, 0.0345, and 0.0313, 0.0450, 0.0380, respectively. R2 values reached 0.9513, 0.9254, 0.9316 and 0.9377, 0.8822, 0.9122 respectively. Compared with the original 6S model and FLAASH model, the mean percent absolute error (MPAE) of the optimized 6S model was reduced by 32.20% and 15.86% for Landsat-8 OLI, respectively. On the other, for the Sentinel-2 MSI SR product, the MPAE value was reduced by 33.56% and 33.32%. For the two kinds of data, the accuracy of each band was improved to varying extents by the optimized 6S model with the auxiliary data. These findings support the hypothesis that reliable auxiliary data are helpful in reducing the influence of the atmosphere on images and restoring reality as much as is feasible.