MERSI is the keystone payload of FengYun-3 and there have been two sensors operating on-orbit since 2008. The on-orbit response changes obviously at reflective solar bands (RSBs) and must be effectively monitored and corrected. However MERSI can not realize the RSBs onboard absolute radiometric calibration. This paper presents a new vicarious calibration (VC) method for RSBs based on in-situ BRDF model, and vector radiometric transfer model 6SV with gaseous absorption correction using MOTRAN. The results of synchronous VC experiments in 4 years show that the calibration uncertainties are within 5% except for band at the center of water vapor absorption, and 3% for most bands. Aqua MODIS was taken as the radiometric reference to evaluate the accuracy of this VC method. By comparison of the simulated radiation at top of atmosphere (TOA) with MODIS measurement, it was revealed that the average relative differences are within 3% for window bands with wavelengths less than 1 μm, and 5% for bands with wavelengths larger than 1 μm (except for band 7 at 2.1 μm). Besides, the synchronous nadir observation cross analysis shows the excellent agreement between re-calibrated MERSI TOA apparent reflectance and MODIS measurements. Based on the multi-year site calibration results, it was found that the calibration coefficients could be fitted with two-order polynomials, thus the daily calibration updates could be realized and the response variation between two calibration experiments could be corrected timely; there are large response changes at bands with wavelengths less than 0.6 μm, the degradation rate of the first year at band 8 (0.41 μm) is about 14%; the on-orbit response degradation is maximum at the beginning, the degradation rates slow down after one year in operation, and after two years the responses even increase at some band with wavelengths larger than 0.6 μm.