To simplify the cross-calibration process and improve calibration frequency and accuracy, this paper proposes a cross-calibration method for the multispectral remote sensor Multi-Spectral Instrument (MSI) carried by Sentinel-2B using the hyperspectral remote sensor, that is, the satellite calibration spectrometer (SCS) carried by Hai Yang (HY)-1C, as the reference sensor and establishes the calibration process. Precise spectral response matching between SCS and MSI spectral channels is performed by the interpolation and iteration of hyperspectral data to eliminate the difference in band settings and significantly improve the accuracy of cross-calibration coefficients. The SNO-x inherited from the simultaneous nadir overpass (SNO) method is used as a prediction method to carry out cross-calibration imaging in mid- and low-latitude regions, which improves the cross-calibration frequency and broadens the dynamic range of calibration. The cross-calibration coefficients and offsets of MSI B1∼B7 and B8a were obtained by processing the earth observation images of the MSI and SCS on January 24, 2019. Then, the cross-calibration coefficients and offsets are applied to the ocean, farmland and other ground objects with different reflectance, and the reliability and accuracy of the cross-calibration results are evaluated with the Moderate-resolution Imaging Spectroradiometer (MODIS) carried by Terra as a reference. To improve the accuracy of the evaluation, the spectral band adjustment factor between the corresponding channels of MSI and MODIS is used to correct the measured reflectance of MODIS based on the satellite calibration coefficient. The reflectance directly obtained by processing the MSI image is used as the MSI-measured reflectance, the reflectance obtained based on the cross-calibration coefficient is used as the MSI-calculated reflectance, and the reflectance corrected by the spectral band adjustment factor (SBAF) is used as the MODIS-calculated reflectance. The results show that the mean root-mean-square relative error (RMSRE) between the MODIS-calculated reflectance and the MSI-calculated reflectance is 2.16% and that the mean RMSRE between the MODIS-calculated reflectance and the MSI-measured reflectance is 3.05%, indicating that the reflectance corrected based on calibration coefficients is closer to the MODIS-calculated reflectance. Finally, each uncertainty source in the cross-calibration is analyzed, and the comprehensive uncertainty is found to be 4.03%, indicating that SCS can be used as a reference for MSI cross-calibration.