Abstract: In order to study the operation stability of solid oxide fuel cell with methane as fuel，10%CuO-Ce0.15Zr0.85O2 was prepared by the co-precipitation method and citric acid sol-gel method，respectively. YSZ electrolyte support planar SOFC with LSM cathode was made with 10%CuO-Ce0.15Zr0.85O2 and NiO/YSZ anode，respectively. XRD and SEM were used to characterize the anode materials and the structure of anode and cathode. The electrical performance of the cell with different anode materials were measured with methane as fuel. The performance to prevent carbon deposition of two Cu-Ce-Zr-O anode materials prepared by different methods were compared with methane as fuel. The anode structure and the electrical performance of citric acid sol-gel Cu-Ce-Zr-O anode was better than co-precipitation one. The long-term stability of two anodes prepared by two different Cu-Ce-Zr-O anode materials were better than conventional Ni-YSZ anode.