Zinc oxide (ZnO) nanostructures have attracted great attention as a promising functional material with unique properties suitable for applications in UV lasers, light emitting diodes, field emission devices, sensors, field effect transistors, and solar cells. In the present work, ZnO nanowires have been synthesized on an n-type Si substrate using a hydrothermal method where surfactant acted as a modifying and protecting agent. The surface morphology, electrochemical properties, and opto-electrochemical properties of ZnO nanowires are investigated by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), cyclic voltammetry, and impedance spectroscopy techniques. The cycling characteristics and rate capability of the ZnO nanowires are explored through electrochemical studies performed under varying electrolytes. The photo response is observed using UV radiation. It is demonstrated that crystallinity, particle size, and morphology all play significant roles in the electrochemical performance of the ZnO electrodes.