Light scattering from rough surfaces remains an important area of interest as it has great potential in a wide variety of fields such as polarized imaging and target identification. Compared to existing simulative methods, the Kirchhoff approximation method offers a much higher calculation efficiency and easy polarization setting that is especially fit for polarized scattering research. In this paper, by studying full angular Stokes vectors via the Kirchhoff approximation from two-dimensional (2D) randomly rough surfaces with various materials, the difference between Stokes vectors of metals and dielectrics is discovered. Moreover, we have successfully explained the distinction between metals and dielectrics by the phase difference between the incident and scattered waves using theoretical analysis. We believe the research could provide an easy and robust criterion for distinguishing metals and dielectrics in various fields such as laser radar and remote sensing.