 An interwoven hollow fiber structured mesoporous NiO catalyst doped with C, S was fabricated by the vacuum impregnation and thermal decomposition methods using eggshell membrane as template. The structure of the catalyst was characterized by X-ray diffraction, thermo-gravimetric analysis, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and specific surface area test. Under a high vacuum condition, the synthesized NiO material has a better interwoven fiber and mesoporous structure, which effectively increases the specific surface area of the material. C and S were doped into NiO via eggshell membrane pyrolysis, which then formed C–OH and SO42− species on the surface of the material. The electrocatalytic performance of the catalyst for the oxidation of methanol in alkaline solution was studied by cyclic voltammetry and chronoamperometry. The C, S doped mesoporous NiO material exhibits much higher catalytic efficiency and anti-poisoning ability than that of NiO nanoparticles due to the synergistic catalysis of NiO and doping C–OH and SO42− species.