The Sentinel-2B offers high spatial resolution optical imagery from 13 bands in the visible, near infrared, and short-wave infrared range of the electromagnetic spectrum, providing enhanced continuity to monitoring global terrestrial surfaces and coastal waters. In this article, its radiometry calibration is evaluated using 37 clear-sky observations in 2018 from the four sites of radiometric calibration network for assuring data quality. However, since the single calibration results acquired under different surface and atmospheric conditions have different biases and different uncertainties, it is difficult to determine which calibration sample is much more trustable. In view of this, by assuming that the calibration samples are independent of each other, a state-of-the-art reference value is derived by combining 37 calibration samples using a weighted average method, which has much lower uncertainty and approaches the “true” value. The reference value also could be used to compare each calibration result. The result shows that the reference value of the relative difference between the simulated and observed top-of-atmosphere reflectance is 4.29%, 4.95%, 4.54%, 5.34%, respectively, for bands 2, 3, 4, and 8, and the corresponding uncertainty is 1.09%, 1.10%, 1.10%, and 1.12%, respectively; the degree of equivalence for each sample is calculated by comparing each calibration result with the reference value. It is worth noting that the degrees of equivalence are lower than 5%, and the four samples on July 9, July 13, October 4, and October 11 perform worse than the other sample.