Efficient production of ammonia using environmentally friendly techniques under ambient conditions is crucial to renewable energy storage and industrial applications, and catalysts with new reaction pathways are highly desirable. In this work, black phosphorus (BP) is used as a metal‐free 2D catalyst for the photoelectrochemical (PEC) nitrogen reduction reaction (NRR). The electrode is fabricated by layer‐by‐layer assembly of BP nanosheets on an indium tin oxide substrate. The PEC NRR activity in the N₂ saturated aqueous electrolyte without a sacrificial agent is excellent, as exemplified by an ammonia yield rate of 102.4 µg h⁻¹ mgcat.⁻¹ and Faradaic efficiency of 23.3% at −0.4 V, which are the best among nonmetal catalysts for synthesis of ammonia by photocatalysis and electrocatalysis. Furthermore, the BP electrode shows excellent stability after 6 consecutive cycles. The excellent PEC catalytic properties are attributed to the light excitation enhanced electrocatalytic process and that the external bias promoted photocatalytic process improves ammonia production synergistically. The results not only demonstrate the great potential of BP in PEC catalysis, but also identify a promising technique to produce ammonia under ambient conditions using solar energy and electric energy.