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The highly ordered TiO2 nanotube arrays (TNTs) were successfully prepared on Ti foil by anodization in ethylene electrolytes containing 0.7 wt% NH4F concentrations and 5 wt% water content at 20V anodization voltage.The length of TNTs was controlled by varying anodization times.Effects of annealing temperature and anodization time on the decomposition of Acid Red 4 (AR4) by photocatalytic (PC) or photoelectrocatalytic (PEC) processes were discussed.