ZnO-based composition structures are widely used nowadays for optical emitters, gas sensors, luminescent materials and materials for nanoelectronics, piezoelectric transducers, catalytic converters etc. Luminescent characteristics of ZnO/ZnSe composition structures are reported below. ZnO/ZnSe composites with various component ratios were synthesized by chemical deposition of zinc oxide to powdered zinc selenide. Equimolar (1:1) solutions of zinc nitrate and hexamethylenetetramine were used for synthesis of zinc oxide. Before starting the synthesis, powdered zinc selenide was introduced into the reaction mixture under continuous stirring that lasted during the all synthesis process in order to provide the composite homogeneity. As a result, the powders with zinc selenide content of 0 %, 6 %, 38 %, and 75 % were synthesized.  Photoluminescence (PL) spectra of the synthesized composites (a) and X-ray pattern for one of the composites (b) are shown in Figure 1. The spectra consist of the PL bands at 420 and 545 nm, which are characteristic for ZnO and are caused by VZn and VO structure defects respectively, and the PL band at 465 nm, which is characteristic for ZnSe and is attributed to self-activation emission caused by uncontrollable (Al, Ga, Cl) and VZn native defects. The intensity of the emission bands is determined by the ratio between ZnO and ZnSe components. It should be pointed out that the solid solutions are not formed, as far as their presence would lead to the appearance of the PL band, the maximum of which would shift with changing composite composition. An additional evidence of this fact is the X-ray pattern for the composite with ZnSe content of 38 % (Fig. 1b). As it is seen, the composite consists of the ZnSe and ZnO fractions. The synthesized composites may be regarded as the heterocontacts of ZnO (Eg = 3.37 eV) and ZnSe (Eg = 2.67 eV) wide band-gap semiconductors [1]. The main feature of this heterocontact is the fact that oxygen does not diffuse into ZnSe lattice and does not promote the formation of solid solutions. The physical model with ZnO being a basis for ZnO/ZnSe composite formation is proposed.