In this work, we attempted to create surface disorder on CaTiO3 nanocuboids by NaBH4 treatment with the aim of enhancing the photocatalytic activity. The samples were systematically investigated by XRD, SEM, TEM, BET, XPS, UV vis DRS, PL, EIS and photocurrent response. The photocatalytic activity of the samples were evaluated by degrading RhB under irradiation of simulated sunlight, UV and visible light. It is demonstrated that NaBH4 treated CaTiO3 samples exhibit an obviously enhanced photocatalytic activity. In particular, the sample treated at 0.1 M NaBH4 solution has a photocatalytic activity ca. 2.0 times higher than pristine CaTiO3. This is ascribed to the fact that the created surface disorder facilitates the separation of photogenerated electron-hole pairs, and thus more photogenerated holes are able to participate in the photocatalytic reactions.