In this paper, CeO₂ with a pore size distribution range of 3.1~4.2nm and a specific surface area of 174.72m₂/g was prepared as a co-catalyst by hydrothermal method. PtNiCeO₂/C catalyst was prepared by microwave assisted glycol method using carbon nanotubes as carrier. Effect of Ni addition on electrocatalytic performance of Pt based catalysts. The prepared CeO₂ and the catalyst were characterized by X-ray diffraction (XRD), BET, SEM and EDAX. The prepared catalyst was characterized by electrochemical workstation electrochemical performance test. The results show that the electrocatalytic activity of CeO₂ catalyst prepared by adding CeO₂ and the ratio of Pt to Ni is 5:1, the electrocatalytic activity is 90.41m₂/g and the peak current density is 837.67A/g, 1100s steady-state current density of 178.33A/g, indicating that adding a certain amount of Ni, can improve the catalyst anti-toxic and electrocatalytic performance.