Developing efficient anode catalysts for direct ammonia solid oxide fuel cells (NH₃-SOFCs) under intermediate-temperatures is of great importance, in support of hydrogen economy via ammonia utilization. In the present work, the pyrochlore-type La₂Zr_2–xNi_xO_7+δ (LZN_x, x = 0, 0.02, 0.05, 0.08, 0.10) oxides were synthesized as potential anode catalysts of NH₃-SOFCs due to the abundant Frankel defect that contributes to the good conductivity and oxygen ion mobility capacity. The effects of different content of Ni²⁺ doping on the crystal structure, surface morphology, thermal matching with YSZ (Yttria-stabilized zirconia), conductivity, and electrochemical performance of pyrochlore oxides were examined using different characterization techniques. The findings indicate that the LZN_x oxide behaves as an n-type semiconductor and exhibits an excellent high-temperature chemical compatibility and thermal matching with the YSZ electrolyte. Furthermore, LZN_0.05 exhibits the smallest conductive band potential and bandgap, making it have a higher power density as anode material for NH₃-SOFCs compared to other anodes. As a result, the maximum power density of the LZN_0.05-40YSZ composite anode reaches 100.86 mW/cm² at 800 °C, which is 1.8 times greater than that of NiO-based NH₃-SOFCs (56.75 mW/cm²) under identical flow rate and temperature conditions. The extended durability indicates that the NH₃-SOFCs utilizing the LZN_0.05-40YSZ composite anode exhibits a negligible voltage degradation following uninterrupted operation at 800 °C for 100 h.