The valence band offsets (VBO) for the b{eta}-type A3B6 layered compounds depending on the thickness of the crystals have been investigated from the first principles, based on the density functional theory. To simulate the structure of a given thickness the periodic slab model was used. Two adjacent crystal slabs consisting of several layers were separated by a vacuum region of two-layer width. It is shown that at the crystal thickness more than 12 layers, photothreshold practically becomes independent on the thickness of the crystal.