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Radiometric calibration is a prerequisite to quantitative remote sensing, and its accuracy has a direct impact on the reliability and accuracy of the quantitative application of remote-sensing data. This article attempts to cross-calibrate the visible and near-infrared channels 1 450–520 nm, 2 520–590 nm, 3 630–690 nm, and 4 770–890 nm of the China–Brazil Earth Resources Satellite CBERS-02B/charge-coupled device CCD camera with channels 3 459–479 nm, 4 545–565 nm, 1 620–670 nm, and 2 841–876 nm of the Terra/Moderate Resolution Imaging Spectroradiometer MODIS, respectively. The radiative transfer modelling RTM method is implemented using the CBERS-02B/CCD and Terra/MODIS measurements at the Dunhuang radiometric calibration site in October 2008. The differences between the cross-calibration and vicarious calibration techniques for channels 1, 2, 3, and 4 are 11.15%, –0.89%, 2.88%, and 11.28%, respectively. Furthermore, the accuracies of the cross-calibration coefficients of CBERS-02B/CCD are analysed, wherein the results indicate that the calibration uncertainty is within 5%.