Aiming at the problems of high false alarm rate and single oil type identification during oil spill detection on the sea surface， based on the Fresnel theory， the polarization degree model of oil spill on rough sea surface under different azimuth angles and zenith angles is established， and its influence on polarization degree distribution is analyzed. A visible light polarization bidirectional reflection distribution test device is set up outdoors， the visible light polarization degree images of four typical marine oil spills， including heavy oil， crude oil， gasoline and diesel are obtained at different azimuth angles and zenith angles. The difference of polarization degree of different oils is analyzed by extracting image gray data， experimental results show that the theoretical model is correct. The experimental results show that the polarization characteristics of visible light are obviously different with different oil spills， and the polarization contrast is generally higher than 5%.The use of visible light polarization to distinguish oil species is a useful supplement to traditional oil spill detection methods and is of great significance to improve the ability of marine pollution control.