Zinc-based materials are currently considered as an alternative for toxic chromium and costly platinum catalysts for propane dehydrogenation. So far however insufficient attention has been devoted to these materials in the literature. In this work we have revealed the nature of active sites in zinc-alumina (γ-alumina) catalysts. We have investigated zinc-alumina catalysts prepared by two different methods: traditional incipient wetness impregnation and zinc chemical vapor deposition (CVD) on alumina. The catalysts were characterized by infrared spectroscopy of adsorbed CO and H2 molecules, TPR measurements and tested in propane dehydrogenation. It has been shown that high-temperature interaction of zinc vapor with alumina results in the formation of surface Zn2+ cations which are active in hydrogen dissociation and propane conversion. The amount of zinc that can be introduced by this procedure depends on the alumina dehydroxylation degree. It has been found that molecular hydrogen heterolytically dissociates on Zn2+ surface cations resulting in the formation of surface zinc hydride species. The Zn2+ sites on the surface of alumina are heterogeneous and are characterized by different band positions in the IR spectra of adsorbed CO and H2 molecules. The Zn2+ sites are subjected to reduction under the reaction conditions.