The directional polarimetric camera (DPC) on-board the GF-5A satellite is designed for atmospheric or water color detection, which requires high radiometric accuracy. Therefore, in-flight calibration is a prerequisite for its inversion application. For large field optical sensors, it is very challenging to ensure the consistency of radiation detection in the whole field of view in the space environment. Our work proposes a vicarious in-flight calibration method based on sea non-equipment sites (visible bands) and land non-equipment sites (all bands). Combined with environmental parameters and radiation transmission calculations, we evaluated the radiation detection accuracy of the 0° to 60° view zenith angle of the DPC in each band. Our calibration method is based on the single-day normalized radiance data measured by the DPC. Through data selection, enough calibration samples can be obtained in a single day (the number of desert samples is more than 5000, and the number of calibration samples of the ocean is more than 2.8×106). The measurements are compared with the simulation of 6SV VRT code or look-up tables. The massive amount of data averages the uncertainty of a single-point calculation. Although the uncertainty of a single sample is significant, the final fitting of the curve of the variation in the radiometric calibration coefficient with the observation angle can still keep the root mean squared error at approximately 2–3% or even lower, and for visible bands, the calibration results for both ocean sites and desert sites are in good agreement regarding the non-uniformity of the sensor.