China’s new generation of polar-orbiting meteorological satellite, Fengyun-3D (FY-3D), is equipped with the MEdium Resolution Spectral Imager II (MERSI-II) sensor, which greatly enhances Chinese capacity for comprehensive space environment detection and meteorological remote sensing. MERSI-II has two mid-infrared (MIR) channels with the potential to apply split-window (SW) algorithms. We have developed an improved nonlinear SW (NSW) algorithm to retrieve the ground brightness temperature T0gb without the contribution of the solar direct beam from MERSI-II MIR data, enabling the accurate retrieval of surface bidirectional reflectivity ρb based on the radiative transfer equation (RTE). Compared with the traditional estimation method, this paper assumed a linear relationship between ρb of MIR channels 20 and 21, and believed that under dry-cool atmospheric conditions, T0gb is not equal. Considering different solar zenith angles (SZAs), by iterating the combination of atmospheric and surface parameters under reasonable variations, the MODerate spectral resolution atmospheric TRANsmittance (MODTRAN) model version 5.2 was used to obtain the simulation datasets for determining the NSW coefficients. In the practical retrieval, the precise algorithm coefficients are only relevant to SZA. The R2 fitted by the NSW algorithm is 0.99, and the root mean square error (RMSE) is less than 0.58 K for different SZAs. Under different SZAs, comparing the actual value of ρb with the proposed method, the bias is less than 1.57×10-3, and the RMSE is less than 2.21×10-3. A detailed sensitivity analysis found that the errors in atmospheric water vapor content (WVC), CO2 concentrations, O3 concentrations, horizontal visibilities, and instrumental noise were below the order of 10-4, and their effects on the retrieval of ρb were negligible. This study employed two methods to validate T0gb, thereby indirectly validating ρb. First, the MODIS land surface emissivity (LSE) product MYD11C1 and the ERA5-Land land surface temperature (LST) product were used to validate T0gb, yielding a bias of 0.9 K and an RMSE of 1.13 K. Second, in situ measurements from the SURFRAD sites were used to validate T0gb, resulting in a bias of 0.74 K and an RMSE of 1.83 K. Overall, results showed that the proposed algorithm has good accuracy and can improve their applications in relevant fields.