Tungsten trioxide nanorods have been generated by the thermal decomposition (450 °C) of tetrabutylammonium decatungstate. The synthesized tungsten trioxide (WO 3) nanorods have been characterized by XRD, Raman, SEM, TEM, HRTEM and cyclic voltammetry. High resolution transmission electron microscopy and X-ray diffraction analysis showed that the synthesized WO 3 nanorods are crystalline in nature with monoclinic structure. The electrochemical experiments showed that they constitute a better electrocatalytic system for hydrogen evolution reaction in acid medium compared to their bulk counterpart.