The polyporous carbon supported tungsten carbide (polyporous C@WC1-x) composite was prepared using hexagonal silica MCM-41 as the hard template by raw material solution impregnation, mechanical milling and simultaneous reduction and carbonization by temperature programming in mixture gas (CH4/H2). The structure and morphology of polyporous C@WC1-x composite were studied via X-ray diffraction, transmission electron microscopy and so on. The electrocatalytic property was tested for the electroreduction of p-nitrophenol (PNP) in neutral media. Results revealed that the composite is consisted of polyporous carbon and nanocrystalline WC1-x, possessing good electrocatalytic activity in the reaction of PNP reduction.