Electrochemical ammonia synthesis is one of the sustainable technologies to artificially synthesize ammonia because of its reduced energy consumption and environmental friendliness. Nevertheless, the low ammonia yield and poor selectivity of the nitrogen reduction reaction limit its large-scale industrial applications. Herein, mesoporous RhRu film on nickel foam (mRhRu/NF) is synthesized by electrodeposition using a diblock copolymer as a soft template. The introduction of the Ru element with a high nitrogen adsorption energy into mesoporous Rh film significantly improves the catalytic performance due to the electronic effect and binder-free mesoporous structure. In a neutral solution, the mRhRu/NF shows a high ammonia production rate of 30.28 μg h⁻¹ mg_cat⁻¹ and a Faraday efficiency of 28.33%. This research offers an inspiring route for the rational synthesis of self-supported mesoporous alloys for active NRR.