Direct one step grating relief formation by laser beam on the surface of amorphous chalcogenide nanomultilayers of the composition As₂S₃-Se was performed. Successive nanolayers on a glass substrate were prepared by thermal vacuum deposition with cyclic motion of substrate. Optical constants were obtained from transmission spectra data in the range of 450-900 nm. The dependence of the surface relief formation on nanomultilayers vs. The polarization states of laser beams was studied. The surface gratings with maximum relief depth were recorded under the two linear polarized beams falling on the sample surface at (+45°)-(-45°). Holographic diffraction gratings with the diffraction efficiency ∼28% value in transmission mode at λ = 0.65 μm were recorded without additional treatment. This fact is explained by the contribution of mass transport whose direction is defined by the electric vector of laser beams. Recorded grating provides high optical quality of the obtained relief with depth of the grooves of about 100 nm at the total structure thickness 2500 nm.