In order to reduce the requirement of the application of polarization imaging technology, a method of material classification under ambient lighting condition is proposed. According to the Fresnel law of reflection, there are some polarization components with the reflected light on target surface. The azimuth angle between detector and reflector is obtained by detecting the polarization angle, horizontal and vertical polarization degree of the detected surface is obtained by compensating the four directions of the polarizer. The target material can be sorted out by measuring degree of polarization of reflected light and reflectivity ratio. The reflection polarization degree and reflectivity ratio of rubber plate and metal plate are simulated and experimental researched, the results show that there is obvious difference of reflectivity ratio between metal and nonmetal in a certain observation angle range, and the metal and nonmetal targets can be distinguished effectively by using Fresnel reflectivity ratio as a discriminated parameter.