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On-orbit radiometric characterization of the multispectral (MS) imagery of the Korea Aerospace Research Institute (KARI)’s Korea Multi-Purpose Satellite-3A (KOMPSAT-3A), which was launched on 25 March 2015, was conducted to provide quantitative radiometric information about KOMPSAT-3A. During the in-orbit test (IOT), vicarious radiometric calibration of KOMPSAT-3A was performed using the Second Simulation of a Satellite Signal in the Solar Spectrum (6S) radiative transfer model. The characteristics of radiometric tarps, the atmospheric optical depth from multi-filter rotating shadowband radiometer (MFRSR) measurements, and sun-sensor-geometry were carefully considered, in order to calculate the exact top of atmosphere (TOA) radiance received by KOMPSAT-3A MS bands. In addition, the bidirectional reflectance distribution function (BRDF) behaviors of the radiometric tarps were measured in the laboratory with a two-dimensional hyperspectral gonioradiometer, to compensate for the geometry discrepancy between the satellite and the ASD FieldSpec (R) 3 spectroradiometer. The match-up datasets between the TOA radiance and the digital number (DN) from KOMPSAT-3A were used to determine DN-to-radiance conversion factors, based on linear least squares fitting for two field campaigns. The final results showed that the R-2 values between the observed and simulated radiances for the blue, green, red, and near-infrared (NIR) bands, are greater than 0.998. An approximate error budget analysis for the vicarious calibration of KOMPSAT-3A showed an error of less than 6.8%. When applying the laboratory-based BRDF correction to the case of higher viewing zenith angle geometry, the gain ratio was improved, particularly for the blue (1.3%) and green (1.2%) bands, which exhibit high sensitivity to the BRDF of radiometric tarps during the backward-scattering phase. The calculated gain ratio between the first and second campaigns showed a less than 5% discrepancy, indicating that the determined radiometric characteristics of KOMPSAT-3A are reliable and useful to the user group for quantitative applications.