In present work the one-step direct relief formation of diffraction gratings using As₂S₃-Se nanomultilayers were studied. We have carried out a study of the polarization sensitive recording properties of the chalcogenide glasses in form of nanomultilayers. Nanomultilayers deposition, samples structure and recording process peculiarities were discussed. The surface relief gratings were patterned into nanomultilayers by method of polarization holography. It was shown that surface relief vector holographic gratings formed by two 45°polarization states and by left-right circular polarizations are phase gratings. The kinetics of diffraction efficiency of both phase and intensity gratings were compared. The possible explanations based on dielectrophoretic forces existing in fluidic systems or H. Fritzche' model supposing the presence of minimum isotropic volume with the anisotropic structural units are discussed. The method offers the advantage of the fabrication of relief structures with one-step processing, without the necessity for any subsequent processing steps.