This paper presents absolute radiometric calibration coefficients (gains) that explain the relationship between the digital number (DN) and at-sensor radiance for the multispectral camera (MSC) on Korea’s first high-resolution satellite (KOMPSAT-2). Absolute radiometric calibration was performed using a reflectance-based method. In addition, the suitability of vicarious results from radiance- and reflectance-based validations was analyzed with reference to IKONOS and QuickBird images. The latter are spectrally similar to KOMPSAT-2 images and have been validated in a large number of studies. For all bands, the values of fitted lines for the gain ranged from 0.82 to 0.94, representing an improvement compared to previous findings for the KOMPSAT-2 MSC. To analyze the suitability of the vicarious results, same-pixel at-sensor radiances across different spectral bands were compared. In all bands, except the red band of QuickBird, the at-sensor radiances of KOMPSAT-2 MSC were highly correlated with those of IKONOS and QuickBird. In addition, same-pixel comparisons of reflectance across different spectral bands showed that the slopes of the least-squares lines for each band were similar to the results of the radiance comparison. The standard deviation among top of atmosphere (TOA) reflectances was within 0.019 for all bands. To calculate the tasseled cap transformation (TCT) coefficients for the KOMPSAT-2 MSC, an empirical method was applied using radiometric normalization. The results were similar to those obtained using the TCT coefficients for IKONOS and QuickBird in the brightness, greenness, and wetness components. The TCT images showed similar patterns. The absolute radiometric calibration coefficients presented here appear to be a good standard for maintaining the optical quality of the KOMPSAT-2 MSC, for which prelaunch, on-board, and vicarious calibration data are lacking.