An expression of the degree of polarization (DOP) based on the geometrical optics polarimetric bidirectional reflectance distribution function model is presented. In this expression, the DOP is related to the surface roughness and decreases at different reflection angles because diffuse reflection is taken into consideration. A shadowing/masking function introduced into the specular reflection expression makes the DOP values decrease as the angle of incidence or observation approaches grazing. Different kinds of materials were measured to validate the accuracy of this DOP expression. The measured results suggest that the errors of the DOP are reduced significantly, and the polarized reflection characteristics can be described more reasonably and accurately.