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For better application of TiO2 nanotube array electrodes in solar cells, TiO2 nanotube arrays were prepared on a titanium substrate in 0.5wt%NH4F/glycerol electrolyte by means of anodic oxidization at a constant potential. The characteristics of the electron transfer and the interface of the TiO2 nanotube array electrodes were researched by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), electron paramagnetic resonance spectrometer (EPR), electrochemical impedance spectra (EIS) and cyclic voltammetry (CV). The impedance curves corresponding to reaction processes of electrodes were determined. Moreover, the dynamic parameters for electron transfer in the electrodes were calculated. The results indicate that the reaction of trivalent titanium compound to tetravalent titanium oxide took place on the surface of the electrodes, leading to great decrease of the resistance of the electrodes. Therefore, the electron pervasion at the electrode-electrolyte interface was accelerated, which was good for the formation of ·OH on the electrode surface