In this work, we report on the metal-insulator transition and electronic transport properties of single crystalline ZnO nanowires synthetized by means of Chemical Vapor Deposition. After evaluating the effect of adsorbed species on transport properties, the thermally activated conduction mechanism was investigated by temperature-dependent measurements in the range 81.7-250 K revealing that the electronic transport mechanism in these nanostructures is in good agreement with the presence of two thermally activated conduction channels. More importantly, it was observed that the electrical properties of ZnO NWs can be tuned from semiconducting to metallic-like as a function of temperature with a metal-to-insulator transition (MIT) observed at a critical temperature above room temperature (T c ∼ 365 K). Charge density and mobility were investigated by means of field effect measurements in NW field-effect transistor configuration. Results evidenced that the peculiar electronic transport properties of ZnO NWs are related to the high intrinsic n-type doping of these nanostructures that is responsible, at room temperature, of a charge carrier density that lays just below the critical concentration for the MIT. This work shows that native defects, Coulomb interactions and surface states influenced by adsorbed species can significantly influence charge transport in NWs.