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NH 3 is an important chemical fertilizer and expecting as H 2 carrier. Several methods have been investigated for eco-friendly NH 3 production under mild conditions instead of Haber-Bosch process using 400 °C, 20 MPa. Here, cyanobacterial Anabaena variabilis was utilized as a nitrogenase-producing biocatalyst that converts N 2 /H 2 O to NH 3 under ambient conditions. Biocatalytic reactions revealed that MV•+ can penetrate cell membrane and transfer electrons generated in inorganic photocatalyst. We first reported photobiocatalytic NH 3 production of cyanobacteria and TiO 2. Comparing with natural system, NH 3 formation rate of the hybrid system increased 81.3 times with an initial rate of 2031.7 nmol·h−1 and turnover number of 216.8. [Display omitted] • Cyanobacteria cultivated in Allen & Arnon medium possess active [MoFe]-nitrogenase. • Photocatalysis of TiO 2 can transfer electrons to both methyl and benzyl viologens. • Only reduce MV•+ can permeate cell envelope and transfer electrons to nitrogenase. • Photobiocatalysis of TiO 2 -cyanobacteria system produces NH 3 from N 2 fixation. [ABSTRACT FROM AUTHOR]