Highly crystalline bismuth titanate (Bi12TiO20, BiT) nanorods, as visible-light photocatalysts were prepared by a template-free hydrothermal process. The as-prepared BiT nanorods fabricated in high yields by simply manipulating pH values in the absence of any capping agent, were characterized by a number of techniques, such as XRD, SEM, TEM, HRTEM, BET, and UV-Vis spectrum. In this case, hydroxide ions seem to play a pivotal role in controlling the formation of seeds and the growth of the BiT nanorods. Based on the structural analysis of nanocrystals obtained at different pH values, we proposed a plausible mechanism to account for the formation of the tunable morphologies. Most importantly, the BiT nanorods with good stability exhibited higher photocatalytic activities in the degradation of Rhodamine B under visible light irradiation (λ ≤ 420 nm) than the commercial P25 TiO 2 and bulk BiT powders, demonstrating that Bi12TiO 20 is a promising candidate as a visible-light photocatalyst.