We report on the synthesis of ZnO nanoparticles and ZnO hierarchical nanorod structures using four different alcohols i.e. methanol, isopropanol, ethanol, and aqueous ethanol (70% alcohol, 30% water). The syntheses of the nanoparticles were carried out by non-aqueous and hydrothermal routes. In general, absolute alcohol allows a better control of the synthesis reaction and nanoparticles as small as 5 nm were obtained, confirmed by TEM. XPS analysis elucidated the chemical states that were correlated to the synthesis reaction. For the nanorod growth, these four alcohols were used as seeding solvents, followed by hydrothermal ZnO nanorod growth. Here, the seed layer tailored the nanorod diameters and surface defects, which were studied by SEM and photoluminescence spectroscopy. Subsequently, the ZnO nanorods were electrically characterized and exhibited persistent photoconductivity under UV irradiation of 365 nm. The differences in conductivity in dark and under UV irradiation were attributed to the size of the nanorods, defect states, semiconductor band bending and oxygen adsorption–desorption mechanisms. Parameters such as photoresponse and photosensitivity are also calculated in order to evaluate their applicability in UV sensors. This work demonstrates optimization of the physical, chemical, electrical and optical properties of both ZnO nanostructures via the use of alcoholic solvents.