Monotungsten carbide and titania nanocomposite with core-shell (WC@TiO2) structure was prepared by a new approach of spray drying and reduction-carbonization reaction, with titania nanopowder and ammonium metatungstate as precursors, methane as carbon source, and hydrogen as reduction gas. The sample was characterized by X-ray diffraction, scanning electron microscope, high resolution transmission electron microscope and X-ray energy dispersion spectroscopy. The results show that its crystal phase is composed of brookite, tungsten and monotungsten carbide. The morphology of the sample particle is irregular sphere-like, with a diameter smaller than 100 nm. Its chemical components are titanium, tungsten, carbon and oxygen. Monotungsten carbide nanoparticles lie on the surface of titania core and form an incomplete shell around titania core in the nanocomposite. The measurement with a microelectrode system of three electrodes shows that the sample is electrocatalytic active to nitrophenol in basic solution at room temperature. Its peak potential is at -0.988 V (vs saturated calomel electrode (SCE)), which is more negative than the peak potential, -0.817 V (vs SCE), of mesoporous monotungsten carbide, and its peak current is 8.809 mu A, which is higher than the peak current, 4.058 mu A, of mesoporous monotungsten carbide. The hydrogen generation potential of the sample is at -1.199 V (vs SCE), which is more negative than that of pure nanosized monotungsten carbide at -1.100 V (vs SCE). These results show that the presence of titania in the sample can lower the peak potential of nitrophenol electrocatalysis and its hydrogen generation potential, and increase its peak current of nitrophenol electrocatalysis in basic solution at room temperature. This indicates a synergistic effect of titania and monotungsten carbide in electrocatalysis.