Bicrystal phase TiO2 nanotubes (NTS) containing monoclinic TiO2-B and anatase were prepared by the hydrothermal reaction of anatase nanoparticles with NaOH aqueous solution and a heat treatment. Their structure was characterized by XRD, TEM and Raman spectra. The results showed that the bicrystal phase TiO2 NTS were formed after calcining H2Ti4O9·H2O NTS at 573K. The bicrystal phase TiO2 NTS exhibit significantly higher photocatalytic activity than the single phase anatase NTS and Dessuga P-25 nanoparticles in the degradation of Methyl Orange aqueous solution under ultraviolet light irradiation, which is attributed to the large surface and interface areas of the bicrystal phase TiO2 NTS.