Hydrogenated TiO2 nanotube arrays exhibit good electrochemical performance, which can be further improved by constructing anatase <001> preferred orientation structure within TiO2 nanotube arrays. The anatase TiO2 nanotube arrays with different degrees of <001> orientation via adjusting the Glycol-H2O ratio in anodization process and the subsequent annealing atmosphere. After electrochemical hydrogenation, the as-prepared samples with different degrees of <001> orientation were characterized by SEM, XPS, XRD, TEM and electrochemical measurements, the effects of preparation process on <001> orientated structure was investigated. The mechanism of the enhanced electrochemical properties by orientated structure orientation was discussed. The hydrogenated TiO2 nanotube arrays with highly <001> orientation delivered the charge specific capacitance as high as 17.31 mF·cm-2, which can attribute to the synergetic effects of hydrogenation and <001> oriented structure.