ZnO photocatalysts were prepared by thermal annealing of zinc acetate, by precipitation reaction of zinc acetate with sodium hydroxide followed by thermal annealing and by precipitation reaction of zinc acetate with sodium hydroxide in the presence of UV irradiation followed by thermal annealing. The prepared nanoparticles were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), UV-Vis diffuse reflectance (UV-Vis DRS) and photoluminescence (PL) spectroscopy, transmission electron microscopy (TEM) and N-2 physisorption measurements. The photocatalytic performance of these materials was investigated for H-2 evolution using aqueous ammonia media under 254 nm UV light. The H-2 evolution was compared with TiO2 Evonik P25. Beside H-2 photocatalytic generation, H-2 photochemical generation was also observed. The different used synthetic procedure leading to the formation of different defects (oxygen vacancies (Vo) and oxygen excess defects (O-i/O-zn)) in the ZnO lattice were factors influencing photocatalytic production of hydrogen. Oxygen vacancy (Vo) was recognized as defect significantly decreasing photocatalyst activity. The highest yields of hydrogen were observed in ZnO prepared by thermal annealing of zinc acetate in air. This photocatalyst possesses the lowest concentration of oxygen vacancies causing efficient trapping of electrons. Consequently higher number of electrons in conduction band was available for photocatalytic reaction. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.