The retrieval of ocean color radiometry from space-based sensors requires on-orbit vicarious calibration to achieve the level of accuracy desired for quantitative oceanographic applications. The approach developed by the NASA Ocean Biology Processing Group (OBPG) adjusts the integrated instrument and atmospheric correction system to retrieve normalized water-leaving radiances that are in agreement with ground truth measurements. The method is independent of the satellite sensor or the source of the ground truth data, but it is specific to the atmospheric correction algorithm. The OBPG vicarious calibration approach is described in detail, and results are presented for the operational calibration of SeaWiFS using data from the Marine Optical Buoy (MOBY) and observations of clear-water sites in the South Pacific and southern Indian Ocean. It is shown that the vicarious calibration allows SeaWiFS to reproduce the MOBY radiances and achieve good agreement with radiometric and chlorophyll a measurements from independent in situ sources. We also find that the derived vicarious gains show no significant temporal or geometric dependencies, and that the mission-average calibration reaches stability after \sim 20–40 high-quality calibration samples. Finally, we demonstrate that the performance of the vicariously calibrated retrieval system is relatively insensitive to the assumptions inherent in our approach.