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Herein we report a simple and easily scalable method for fabricating ZnO/<i>h</i>-BN composites with tunable photoluminescence (PL) characteristics. The <i>h</i>-BN support significantly enhances the ultraviolet (UV) emission of ZnO nanoparticles (NPs), which is explained by the ZnO/<i>h</i>-BN interaction and the change in the electronic structure of the ZnO surface. When <i>h</i>-BN NPs are replaced with <i>h</i>-BN microparticles, the PL in the UV region increases, which is accompanied by a decrease in visible light emission. The dependence of the PL properties of ZnO NPs on the thickness of <i>h</i>-BN carriers, observed for the first time, is explained by a change in the dielectric constant of the support. A quantum chemical analysis of the influence of the <i>h</i>-BN thickness on the electron density redistribution at the <i>w</i>ZnO/<i>h</i>-BN interface and on the optical properties of the <i>w</i>ZnO/<i>h</i>-BN composites was carried out. Density functional theory (DFT) calculations show the appearance of hybridization at the <i>h</i>-BN/<i>w</i>ZnO interface and an increase in the intensity of absorption peaks with an increase in the number of h-BN layers. The obtained results open new possibilities for controlling the properties of ZnO/<i>h</i>-BN heterostructures for various optical applications.