To satisfy the demand of multilayer films on polarization detection, polarized bidirectional reflectance distribution function of multilayer films on slightly rough substrate is established on the basis of first-order vector perturbation theory and polarization transfer matrix. Due to the function, light scattering polarization properties are studied under multi-factor impacts of two typical targets-monolayer anti-reflection film and multilayer high-reflection films. The result shows that for monolayer anti-reflection film, observing positions have a great influence on the degree of polarization, for the left of the peak increased and right decreased compared with the substrate target. Film target and bare substrate can be distinguished by the degree of polarization in different observation angles. For multilayer high-reflection films, the degree of polarization is significantly associated with the number and optical thickness of layers at different wavelengths of incident light and scattering angles. With the increase of the layer number, the degree of polarization near the mirror reflection area decreases. It reveals that the calculated results coincide with the experimental data, which validates the correctness and rationality of the model. This paper provides a theoretical method for polarization detection of multilayer films target and reflection stealth technology.