The Pt-like behavior and synergistic effect of tungsten carbides (WCs) are increased with decreased size and affected by their morphology. However, achieving high specific surface areas of nanostructured WCs with a small size and controlled morphology remains a considerable challenge. In the present studies, WC nanorods with a diameter and length of approximately 50 and 100–300 nm, respectively, were prepared. The morphology of the obtained WO3·H2O was controlled by adding citric acid to the reaction solution. The secondary growth of WO3·H2O crystals was efficiently restrained because double-walled carbon nanotubes were homogenously dispersed in the solution. When the WO3·H2O nanorods were heated in air and carbonized in a nitrogen atmosphere, small-sized WC nanorods with a high specific surface area (32.2 m2 g−1) were obtained. Furthermore, the obtained catalysts displayed improved electrocatalytic activity and stable anti-poisoning performance when the WC nanorods were used as a support for loading platinum nanoparticles. All these results indicate the potential application of WC nanorods in electrochemistry and related fields.