TiO2(B)/anatase heterostructure nanofibers decorated with anatase nanoparticles have been readily synthesized. They showed 3.5-fold higher photocatalytic activity than TiO2(B) towards methanol oxidation. The flatband potential of TiO2(B) is located ca. 200 mV more cathodically than that of anatase. The facile interfacial charge transfer between TiO2(B) and anatase has been confirmed by electrochemical impedance spectroscopy measurements.