General design of polarization-selective volume holograms is discussed in detail. The required diffraction angles for these highly polarization-selective elements are calculated. An effective indexmodulation parameter is defined and used to calculate the required index-modulation value at any specified operating wavelength. Design examples of operating wavelengths at 780, 830, 1050, 1300, and 1550 nm are given. Highly polarization-selective substrate-mode grating pairs for 780-nm operation were fabricated to verify the idea. These elements are suitable for applications in optical switching networks and magneto-optic data storage systems.