A novel and facile approach to prepare black TiO 2 nanoparticles has been developed using cetyltrimethyl ammonium bromide (CTAB) as structure guiding agent. CTAB has played a crucial role in the formation process of TiO 2 nanoparticles by altering the morphology and pore structures, promoting the generation of oxygen vacancies and effectively improving the visible light absorption intensity. Synthetic black TiO 2 -CTAB-300 °C nanoparticles have a high crystallinity with regular mesoporous structure, possessing small particle size, high surface area, and an efficient response to broadband light covering the entire UV–vis-near IR spectrum. Moreover, as-prepared black TiO 2 -CTAB-300 °C nanoparticles showed higher photocatalytic H 2 generation activity under visible light compared with control TiO 2 . [ABSTRACT FROM AUTHOR]