We report nanostructured TiO2/boron-doped diamond (BDD)/Ta multilayer films and their electrochemical performances as supercapacitor electrodes. The BDD films were grown on Ta substrates using electron-assisted hot filament chemical vapor deposition. Ti metal layers were deposited on the BDD surfaces by radio frequency magnetron sputtering, and nanostructured TiO2/BDDITa thin films were prepared by electrochemical etching and thermal annealing. The successful formation of TiO2 and Ta layered nanostructures was demonstrated using scanning electron and transmission electron microscopies. The electrochemical responses of these electrodes were evaluated by examining their use as electrical double-layer capacitors, using cyclic voltammetry, and galvanostatic charge/discharge and impedance measurements. When the TiO2/BDDITa film was used as the working electrode with 0.1 M Na2SO4 as the electrolyte, the capacitor had a specific capacitance of 5.23 mF cm(-2) at a scan rate of 5 mV s(-1) for a B/C ratio of 0.1% w/w. Furthermore, the TiO2/BDDITa film had improved electrochemical stability, with a retention of 89.3% after 500 cycles. This electrochemical behavior is attributed to the quality of the BDD, the surface roughness and electrocatalytic activities of the TiO2 layer and Ta nanoporous structures, and the synergies between them. These results show that TiO2/BDDITa films are promising as capacitor electrodes for special applications. (C) 2015 Elsevier B.V. All rights reserved.