AbstractElectrochemical synthesis of ammonia via nitrogen reduction reaction is a rational route to save energy and relieve pollution compared to the traditional Haber‐Bosch process. In this report, ZrO₂ nanosphere derived from thermolysis of Zr‐based biphenyl‐4,4′‐dicarboxylic acid MOFs (ZrO₂/C) as a non‐noble metal catalyst with large specific surface area and porous structure is proposed to fix nitrogen to ammonia at ambient conditions. Such catalyst achieves Faradaic efficiency of 11.86 % and a NH₃ yield rate of 10.72 μg h⁻¹ mg⁻¹_cat. at −0.6 V vs. the reversible hydrogen electrode in 0.1 M Na₂SO₄. First‐principles calculations confirm the alternating reaction at the catalyst surface.