The photocatalytic nitrogen reduction reaction (NRR) in aqueous solution is a green and sustainable strategy for ammonia production. Nonetheless, the efficiency of the process still has a wide gap compared to that of the Haber-Bosch one due to the difficulty of N 2 activation and the quick recombination of photo-generated carriers. Herein, a core-shell Bi@Bi 2 MoO 6 microsphere through constructing Schottky junctions has been explored as a robust photocatalyst toward N 2 reduction to NH 3 . Metal Bi self-reduced onto Bi 2 MoO 6 not only spurs the photo-generated electron and hole separation owing to the Schottky junction at the interface of Bi and Bi 2 MoO 6 but also promotes N 2 adsorption and activation at Bi active sites synchronously. As a result, the yield of the photocatalytic N 2 -to-ammonia conversion reaches up to 173.40 μmol g -1 on core-shell Bi@Bi 2 MoO 6 photocatalysts, as much as two times of that of bare Bi 2 MoO 6 . This work provides a new design for the decarbonization of the nitrogen reduction reaction by the utilization of renewable energy sources.