Vicarious calibration is a well-developed method for electro-optical (EO) sensor calibration that has been used since the early 1980s. The radiometric calibration of reflectance solar band is mainly applied to reflection inversion. In this paper, a radiometric calibration-reflectance inversion (RCRII) model is proposed as an improved vicarious calibration method. Taking the reflectance of grayscale targets with constant spectrum, suitable uniformity, and near-Lambertian characteristics as the known information, the grayscale target calibration is realized, and the initial value of calibration coefficient and offset are calculated. Then, the adjacency effect is evaluated and corrected by reflectance inversion, and the results are fed back to the calibration process to realize the iterative process of calibration inversion rescaling. The results indicate that the absolute difference between the reflectance calculated with the RCRII model and measured reflectance is less than 0.01. By comparing with Sentinel-2A images, it is cross-verified that the difference of radiance between them is within 4%, and the absolute reflectance difference is less than 0.01, in the range of 0.1~0.3 reflectance.