Anatase TiO₂ photocatalysts with exposed (001) facets have attracted great attention for environmental protection technology due to their high reactivity for degradation of organic species. In this work, potassium hydrogen phthalate (denoted as KHP), as the most commonly used reference standard solution for calibrating photoelectrochemical chemical oxygen demand (denoted as PeCOD) instrument, was selected as the study sample. The intrinsic degradation kinetics of KHP on (001) surface was investigated by a photoelectrochemical (denoted as PEC) method with a purposely (001) faceted double-layered structure TiO₂ photoanode. The high kinetics constants of fast process of KHP and other acids indicate that the (001) surface possesses a higher reactivity of aromatic carboxylic acid as theoretically predicted. Meanwhile, the investigation of the KHP adsorption properties on A001 photoanode provides the possibility of using this photoanode as a sensor in a new type of PeCOD instrument for organic acid determination.