Realizing nitrogen reduction reaction (NRR) to synthesis NH3 under mild conditions has gained extensive attention as a promising alternative way to the energy-and emission-intensive Haber-Bosch process.Among varieties of potential strategies,photoelectrochemical (PEC) NRR exhibits many advantages including utilization of solar energy,water (H2O) as the hydrogen source and ambient operation conditions.Herein,we have designed a solar-driven PEC-NRR system integrating high-efficiency Fe2O3-based photoanode and atomically dispersed cobalt (Co) cathode for ambient NH3 synthesis.Using such solar-driven PEC-NRR system,high-efficiency FeaO3-based photoanode is responsible for H20/OH-oxidation,and meanwhile the generated photoelectrons transfer to the single-atom Co cathode for the N2 reduction to NH3.As a result,this system can afford an NH3 yield rate of 1021.5 μg mgCo-1 h-1 and a faradic efficiency of 11.9％ at an applied potential bias of 1.2V (versus reversible hydrogen electrode) on photoanode in 0.2 mol/L NaOH electrolyte under simulated sunlight irradiation.