ABSTRACTTiO2 Nanotube arrays (TNA) and WO3-coated TNA photoelectrodes were fabricated using an in situ anodization and pulse electrochemical deposition technology. The performance of the TNA photoelectrodes in the photocatalytic (PC) and photoelectrocatalytic (PEC) degradation of 4-nonylphenol (4-NP) was investigated. The effects of the initial pH and the anions on the degradation rates and reaction mechanism of 4-NP were studied by the photoluminescence (PL) spectra and electrochemical impedance spectra (EIS). The degradation of 4-NP was fitted to a first-order reaction, and the apparent kinetic constants were 1.9 × 10−2 min−1 for TNA photoelectrodes and 2.4 × 10−2 min−1 for WO3/TNA photoelectrodes. When a bias potential of 1.0 V was applied, the values for TNA and WO3/TNA photoelectrodes increased to 2.5 × 10−2 and 3.0 × 10−2 min−1, respectively. The degradation of 4-NP was controlled by a charge-transfer process one. WO3-decorated TNA photoelectrodes could increase the adsorption of 4-NP and promote its degradation. For the TNA and WO3/TNAs photoelectrodes, acid and alkaline solutions could facilitate the formation of hydroxyl radicals, whereas the removal of 4-NP was inhibited. The presence of , Cl−, and has a negative effect on the formation of •OH, so did the removal of 4-NP. For the TNA photoelectrodes, the inhibition effect of on the formation of hydroxyl radicals and the removal of 4-NP was the most serious compared with that of , Cl− and , while for the WO3/TNA photoelectrodes the inhibition effect of on the removal of 4-NP was maximum.