Black titania spheres (H-TiO2-x) were synthesized via a simple green method assisted by water plasma at a low temperature and atmospheric pressure. The in situ production of highly energetic hydroxyl and hydrogen species from water plasma are the prominent factors in the oxidation and hydrogenation reactions during the formation of H-TiO2-x, respectively. The visible-light photocatalytic activity toward the dye degradation of H-TiO2-x can be attributed to the synergistic effect of large-surface area, visible-light absorption and the existence of oxygen vacancies and Ti3+ sites.