AbstractFor photoelectrocatalytic cells, a limitation exists in finding appropriate photoelectrode configurations that couple efficient extraction of high‐energy electrons from absorbed photons and selective catalysis. Here we report an organic p‐n junction approach to fabricate molecular photoelectrodes for conversion of solar energy and nitrate into valuable ammonia product. Solar irradiation of the photoelectrode generates charge‐separated states with electrons and holes spatially separated at the n‐type and p‐type components, as revealed by surface photovoltage mapping, at a quantum yield of 90 %. The high‐flux photogenerated electrons are rapidly transferred to the catalyst for solar ammonia production from nitrate reduction at an external quantum efficiency (EQE) and an internal quantum efficiency (IQE) of 57 % and 86 %, respectively. Time‐resolved spectroscopic studies reveal that the large IQE originates from the combined high efficiencies for photoelectron generation, catalyst activation and dark catalysis. In a flow‐cell setup coupled with a silicon solar cell, the photoelectrode without bias generates photocurrent of 57 mA cm−2 and ammonia at an EQE of 52 %.