The electrocatalytic nitrogen reduction reaction (NRR) to ammonia is a promising technology to store renewable energy and mitigate greenhouse gas emissions. However, it usually suffers from low ammonia yield and selectivity because of the lack of efficient electrocatalysts. Herein, we report that the construction of metal phosphide heterojunctions is an efficient strategy for NRR activity enhancement. A CoP–MoP heterojunction electrocatalyst, which is fabricated by a facile NaCl template-assisted strategy, exhibits a favorable ammonia yield rate of 77.8 μg h⁻¹ mg_cat⁻¹ (38.9 μg h⁻¹ cm⁻²) and a high faradaic efficiency of 11.16% at −0.50 V versus the reversible hydrogen electrode. The high NRR electrocatalytic activity can be attributed to the electronic coupling effects and interfacial synergistic effects of CoP and MoP at the heterojunction interface, which accelerates the electron transfer rate. Moreover, Mo doping changes the d-band centers of metal sites on the CoP surface, which is conducive to N₂ adsorption and promotes N₂* adsorption in the competition of occupying active sites, thus inhibiting the HER. This work manifests the high potential of phosphide electrocatalysts and opens an alternative route toward NRR electrocatalysis.