The widely utilization of pharmaceutical and personal care products (PPCPs) in the pharmaceutical therapies and agricultural husbandry has led to the worldwide pollution in the environment. In this study, the photoelectrocatalytic (PEC) behaviors of typical PPCPs, tetracycline (TC), were performed via a highly effective TiO(2) nanopore arrays (TNPs) electrode, comparing with electrochemical (EC) and photocatalytic (PC) process. A significant photoelectrochemical synergetic effect in TC degradation was observed on the TNPs electrode and the rate constant for the PEC process of TNPs electrode was approximately 6.7 times as high as its PC process. The TC removal rate achieved approximately 80% within 3h PEC reaction by TNPs electrode, which is approximately 25% higher than that obtained for a conventional coated TiO(2) nanofilm electrode fabricated by sol-gel method. The possible mechanism involved in the PEC degradation of TC by TNPs electrode was discussed. Furthermore, the TNPs electrode also shows enhanced photocurrent response compared with that for the coated TiO(2) nanofilm electrode. Such kind of TiO(2) nanopores will have many potential applications in various areas as an outstanding photoelectrochemical material.