The vertically aligned multiwalled carbon nanotube (MWCNT) arrays on tantalum foils were successfully coated with TiO2 nanoparticles by a hydrothermal process. The prepared TiO2/MWCNT hybrid was characterized by scanning electron microscopy and transmission electron microscopy. The charge transfer properties and photocatalytic degradation of rhodamine B with and without bias potential under UV irradiation were investigated. The MWCNTs promoted the separation of photoinduced carriers in the TiO2, thus enhanced photocatalytic activity. Applying bias potential on the photoanode further enhanced its catalytic activity. The efficient charge transportation and high photoelectrocatalytic activity towards degradation of rhodamine B made this hybrid material promising for photocatalyst and for the development of photoelectrical devices. (C) 2010 Elsevier Ltd. All rights reserved.