TiO2 nanowire/nanotube electrodes were synthesized by anodization of titanium foils in ethylene glycol solution containing 0.5 wt% NH4F and 1 wt% water at 60 V for 6 h. The microstructure and morphology of the asprepared electrodes were investigated by XRD and SEM. A possible formation mechanism and oxidation parameters of nanocomposite structure were discussed. The relationship between structural characteristics of TiO2 nanowire/nanotube electrodes and its photoelectrochemical characterization were evaluated by electrochemical analyzer and photocatalytic degradation of methylene blue (MB) solution. Furthermore, these TiO2 nanowire/nanotube electrodes promoted the photoelectrochemical characterization due to the larger surface areas, enhanced light harvesting and electron transport rate. The results show that photocurrent density of 1.44mA/cm2 and photocatalytic degradation of 95.51% was achieved for TiO2 nanowire/nanotube electrodes, which were 0.55mA/cm2 and 20.52% higher than the TiO2 nanotube electrodes under a similar condition, respectively.