Amorphous chalcogenide films possess properties suitable for preparing of complex diffraction structures. Particularly, the high resolution of recording and effective structural changes induced by optical or electron beam irradiation should be mentioned. Thin films of As2S3 prepared by thermal deposition technique were used for electron-beam recording of superimposed diffraction gratings. Recording of grating structures was performed with a 25 keV electron beam using a scanning electron microscope BS 300 (Tesla). The dose of irradiation was about 0.7 mC/cm2. A set of pairs of superimposed gratings of equal grating period (Λ=2 μm) with different mutual orientation angles was recorded. In the case of straight-line grating the gratings mutual orientation angle is equal to their lines intersection angle (β). Its value ranged from 2º to 90º. The surface relief diffraction structures were prepared by chemical etching in KOH water solution. The surfaces of relief structures were studied in atomic force microscope (AFM). Of particular interest are pairs of superimposed gratings formed at small angles β. In this case the diffraction structure is formed by periodically alternated striped parts, which consist mainly either separated grating lines, or overlapped grating lines. Decrease of β values results in broadening of such striped parts of grating structure. For example, the grating structures formed at β=4° (a) and β=3° (b) are presented in Fig 1. Here dark lines represent the grooves formed by chemical etching of e-beam irradiated areas of As2S3 film. In the case of β=3° (Fig. 1b). The width of the structure part of separated lines is about 10 μm. The pair of superimposed gratings produces diffracted beams corresponding to both diffraction gratings. In the case of small angle β diffraction pattern is significantly compressed along with grating lines direction in comparison with the case of β=90°. The lowest angle β, that ensured detection of two separated first order diffracted laser beams was equal to 3°. It is reasonable to assume, that such angular resolution detection of diffracted beams will be higher for lower grating period value. The first order diffraction efficiency (DE) of superimposed gratings was measured. It was not revealed any significant dependence DE on β. In addition to recorded superimposed gratings a set of gratings was formed by periodically spaced nodes of line intersections. Corresponding light spots were clearly seen in the diffraction patterns.