Polarization gratings are space-variant subwavelength-structured photonic devices that control electromagnetic wave propagation by local modulation of the state of polarization of light. Using electron beam lithography, we have fabricated such devices in the form of dielectric and metallic surface-relief profiles for operation in the visible wavelength region, where structural features with dimensions on the order of 100 nm are required. We provide experimental demonstrations of various laser-beam splitting elements with diffraction efficiencies exceeding values that could be achieved by diffractive elements operating in the framework of scalar optics.