The feasibility of conventional polarization-selective substrate-mode holograms is usually limited by the finite refractive index modulation strength. Therefore, in this study, a novel design of polarization selective element with a large diffraction angle is proposed based on the coupled-wave theory. The polarization selective element for 632.8nm is fabricated with VRP-M silver-halide recording material. The diffraction efficiencies of s- and p- components are 83% and 5%, and the calculated extinction ratios are 5.58 and 275, respectively. Polarization selective elements fabricated by the proposed method have all the merits of conventional substrate-mode hologram but not limited by the finite refractive index modulation of common recording materials.