In this paper, three-dimensionally ordered macroporous (3DOM) N-doped anatase TiO₂ (N-TiO₂) photocatalysts with well-defined macroporous skeletons were prepared using a simple one-step colloidal crystal-templating method. Organic ammonia ethanediamine was used as the nitrogen source during preparation to enhance nitrogen incorporation into the TiO₂ lattice. The photocatalytic performance of the as-prepared 3DOM N-TiO₂ was investigated by measuring the degradation of rhodamine B (RhB) and the generation of H₂ from water splitting under simulated visible-light conditions. In comparison with the pure TiO₂ and N-doped TiO₂, the results of photodegradation and photocatalytic hydrogen generation reactions showed that the 3DOM N-TiO₂ sample exhibited excellent catalytic activity under visible-light irradiation. In addition, various analytical techniques have been used to characterize the crystal phase, morphology and optical absorption of the obtained samples. The results showed that the 3DOM N-TiO₂ catalyst was successfully synthesized by the one-step colloidal crystal-templating method, and the as-prepared samples possessed well-defined 3DOM skeleton structure, high crystallinity and enhanced visible-light-driven photocatalytic activities.