We report here the effect of the photoelectrochemical photocurrent switching (PEPS) observed on highly-ordered pristine anodized Ti/TiO₂ for the first time. At negative potential bias, blue irradiation gives cathodic photocurrent, whereas anodic photocurrent was observed for ultraviolet irradiation. We believe this phenomenon is due to the electron pathway provided by Ti³⁺ defect states.