Organic pollution is a great threat to the environment and human beings. Photoelectrocatalytic (PEC) degradation has emerged as an effective strategy to remove organic pollutants. In this study, a p-Co3O4/n-TiO2 nanopine arrays-based PEC electrode is prepared on carbon cloth (CC) by a one-step hydrothermal method. Due to the heterojunction and nanopine-like structure, the resulting CC@Co3O4/TiO2 exhibits excellent photocatalytic performance and high capacitance. The charged CC@Co3O4/TiO2 exhibits superior photodegradation ability under visible light. Using tetracycline hydrochloride (TC) as a model pollutant, the degradation kinetic constant of SD-PEC increased to ∼200 % (60 min) by the traditional photocatalytic process (PC). The superior degradation ability of the synthesized arrays is attributed to the p-n junction between Co3O4 and TiO2. In addition, during the charging process, the Fermi level of Co3O4 relative to the O/R energy level of the solution shifts downward. The holes (h+) trapped in the Co3O4 valence band migrate to the solid-liquid interface by the charging process and subsequently participates in the catalytic reaction. This work provides a new route for developing high-performance photocatalysts in the rapid degradation of pollutants.