The invention discloses a Ni/CeO2NP@PANI core-shell structural composite material and a preparation method thereof. The method comprises the following steps: firstly, Ni/CeO2 NPs are prepared througha hydrothermal method; and then aniline is polymerized on the surfaces of the Ni/CeO2 NPs by adopting a chemical oxidation polymerization method, and in the polymerization process of the aniline, through changing a concentration of HCl, conversion from a Ni/CeO2NP@PANI core-shell structure to a spaced Ni/CeO2NP@PANI core-shell structure to PANI hollow spheres is realized. In the process, templatesare not needed, the method is green and environmentally friendly, the preparation method is simple, the preparation process is safe, the energy consumption is low, and the operability is strong; andthe Ni/CeO2 NPs prepared by the method have rough surfaces, so that the specific surface area can be increased to increase the contact area of the Ni/CeO2 NPs and the PANI, and the diffusion of ions and electrons can be promoted to effectively improve the electrochemical performance.