Mesoporous black Ti3+/N-TiO2 spheres with high crystallinity are fabricated by a facile evaporation-induced self-assembly (EISA) method, using urea as nitrogen resource, combined with a mild calcinations (350°C) after an in-situ hydrogenation under an argon atmosphere. The prepared materials are characterized by X-ray diffraction, Raman, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results indicate the prepared sample is uniform mesoporous black Ti3+/N-TiO2 spheres with high crystallinity of anatase, high surface area of ∼100m2g−1, large pore size of 6.5nm and narrow band gap of 2.11eV, could be easily controlled with the diameter from 200 to 800nm. Meanwhile, the photoresponse extends to near-infrared region owing to Ti3+ and N codoping. The visible-light-driven photocatalytic degradation ratio of methyl orange is up to 96% and photocatalytic hydrogen production rate is ∼150μmolh−1, which are several times higher than that of pristine TiO2. Besides, the possible photocatalytic mechanism is proposed. The excellent photocatalytic activity can be ascribed to N and Ti3+ doping resulting in high visible light utilization and enhanced separation of photogenerated charge carriers, and the mesoporous networks offering more surface active sites.