The electrodeposition of lead dioxide (PbO2) in a Ti/TiO2 nanotube (TiO2 NT) array was achieved using a galvanostatic method at room temperature. The formation and growth of PbO2 inside the TiO2 NTs was followed as a function of the deposition time (t(d)). The TiO2 NT: :PbO2 (x s) samples, as well as the TiO2 NTs previously prepared by anodization of Ti sheets, were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD) techniques. It was found that PbO2 formation starts at the bottom of TiO2 nanotubes and grows inside them until a well-dispersed deposit is achieved (t(d) < 5 s) or until formation of PbO2 crystalline deposits or cauliflower-like clusters outside the TiO2 NTs at t(d) > 10 s. In any case, the PbO2 deposit always partially covered the TiO2 NT arrays. Photochemical activity results showed that TiO2 NT::PbO2 (x s) samples had higher photocurrent density values than TiO2 NTs. They also had better photoconversion efficiencies, which strongly suggest the occurrence of a photoelectro-synergistic effect due to electronic transfer assisted by the close contact between TiO2 and PbO2. This assumption was supported by the catalytic bleaching of methyl red (MR) dye solutions. Electrocatalytic (EC) and photoelectrocatalytic (PEC) results showed that, although the discoloration process is not entirely PEC dependent, its contribution is greater than the sum of the individual photocatalytic (PC) and EC processes, which confirms the synergic effect produced by the combination of TiO2 and PbO2 in a nanostructured array. (C) 2013 Elsevier B.V. All rights reserved.