Directional polarimetric camera (DPC) is used to monitor several parameters related to the global atmospheric aerosol and clouds as it can detect atmospheric multi-angle polarization. However, it is an ultra-wide-angle optical instrument; therefore, the polarization effect of lens cannot be neglected, and it should be corrected during the calibration stage. A polarization measurement performance test is conducted prior to launching the instrument in the laboratory and outfield. To meet the requirement of an on-orbit measurement, an on-orbit detection method is designed to assess the polarization detection performance of the optical polarization remote sensing instrument with a large field of view. The rapid evaluation of polarization detection performance in full field of view is achieved by analyzing the polarization rainbow data of ocean flares and water clouds in a wide range of complex environments, and the data processing effectiveness of ground application system is verified. The on-orbit polarization detection performance of DPC is consistent with the laboratory and outfield data, which provides an important basis for aerosol and cloud inversion applications. Furthermore, the detection methods in each stage can be used as a reference in wide-angle polarization remote sensing applications.