tTiO2(B) nanofibres, TiO2(B)/anatase heterostructure nanofibres, TiO2(B)/anatase heterostructure nanofi-bres decorated with anatase nanoparticles, and thermally highly stable anatase TiO2nanorods have beenprepared by hydrothermal treatment of TiO2P25 in aqueous NaOH solution followed by controlled ion-exchange and thermal annealing processes. The obtained TiO2nanomaterials were characterized by x-raydiffraction, scanning electron microscopy, transmission electron microscopy, diffuse reflectance spec-troscopy, electrochemical impedance spectroscopy, and nitrogen adsorption. The photocatalytic activitiesof the prepared materials were quantified by measuring the photocatalytic methanol oxidation underUV–vis illumination. The results indicated that TiO2(B)/anatase heterostructure nanofibres decoratedwith anatase nanoparticles (84% anatase and 16% TiO2(B)) exhibit 3.5-fold higher photocatalytic activitytowards methanol oxidation than TiO2(B) nanofibres and anatase TiO2nanorods. These nanofibres evenshowed higher photocatalytic activity than TiO2P25. This is explained by a better separation of the pho-togenerated charge carriers and, most likely, by the facile interfacial charge transfer between TiO2(B) andanatase structures as confirmed by impedance spectroscopy measurements.