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Atmospheric nitrogen fixation using a photocatalytic system is a promising approach to produce ammonia. However, most of the recently explored photocatalysts for N 2 fixation are in the powder form, suffering from agglomeration and difficulty in the collection and leading to unsatisfactory conversion efficiency. Developing efficient film catalysts for N 2 photofixation under ambient conditions remains challenging. Herein, we report the efficient photofixation of N 2 over a periodic WS 2 @TiO 2 nanoporous film, which is fabricated through a facile method that combines anodization, E-beam evaporation, and chemical vapor deposition (CVD). Oxygen vacancies are introduced into TiO 2 nanoporous films through Ar annealing treatment, which plays a vital role in N 2 adsorption and activation. The periodic WS 2 @TiO 2 nanoporous film with an optimized WS 2 content shows highly efficient photocatalytic performance for N 2 fixation with an NH 3 evolution rate of 1.39 mmol g −1 h −1 , representing one of the state-of-the-art catalysts.