To enhance the accuracy and stability of FY-4A/AGRI detection data, the MODIS, with highly accurate onboard calibration, is selected as the reference sensor for cross-radiation calibration calculations. The following are the data selection conditions: full considered time, observation geometries, field angles, cloud cover, etc. FY-4A/AGRI and Aqua-MODIS image data are selected as matching sample region locations, where the time difference between the observations for the same ground object is less than 15 min, the satellite zenith angle is less than 30°, and the field angle difference is less than 0.01. The 245 collected reflectance spectral curves are convolved with the spectral response functions of the two sensors, and the spectral band adjustment factors of the corresponding bands are calculated for spectral correction purposes. The cross-calibration coefficients for the red and near-infrared bands are calculated by linearly fitting the simulated top of the atmosphere reflectance values and digital number values from the AGRI sensor in a homogeneous area. In this paper, 16 cross-calibration calculations are performed on FY-4A/AGRI image data from August 2018 to September 2020, and the results are compared with the original calibration coefficients to test the feasibility of the proposed method. Additionally, 31 cross-calibration calculations are performed on image data from October 2020 to December 2022 to study the resulting AGRI sensor quality and performance changes. The NDVI of the FY-4A/AGRI image data was calculated before and after the cross-radiometric calibration using the maximum synthesis method. Additionally, the NDVI of the MODIS image data was compared and analyzed from three aspects: time, space, and the change trend. The results show that the spectral band adjustment factor calculated using the reflectance spectral curves of the ground objects in this paper can effectively correct for the spectral differences between the two sensors. Sixteen cross-calibration coefficients are less than 5.2% different from the original calibration coefficients, which fully proves the feasibility of the method used in this paper. All of the cross-calibration results show that the AGRI sensors have a certain degree of attenuation in the red and near-infrared bands, and the annual attenuation rates are approximately 1.37% and 2.55%, respectively. Cross-radiometric calibration has further improved the quality of the NDVI in FY-4A/AGRI imagery, enhancing the precision of its data application.