We report for the first time the nitrogen doping of reduced graphene oxide (rGO) and TiO2 nanowires (NWs) when TiO2 NWs intercalated rGO membranes were immersed in ammonia aqueous solution under 8 W 254 nm UV irradiation. Such nitrogen-doped rGO/TiO2 NWs photocatalytic membrane produced H2 at a rate of 208 μmol h−1 g−1 under 8 W 254 nm UV irradiation, which is more than 14 times higher than the yield of the TiO2-P25 and 30-fold higher than TiO2 NWs alone under the same condition. Our study demonstrates a new synthesis route for doping nitrogen in rGO and TiO2, as well as the preliminary feasibility of hydrogen extraction from ammonia-containing wastewater with such a low-cost recyclable photocatalyst. In addition, the study illustrates the complexity of photocatalysis of ammonia aqueous solution, which involves multiple reactions in concurrence.