We report on Ni-modified TiO2 nanotubes with improved photocatalytic properties. Using the as-anodized TiO2 nanotubes as templates, Ni was electrodeposited using pulsed current waveforms. It was found that the Ni deposition was first initiated at the bottoms of the intertubular voids and then grew upward, resulting in a Ni/TiO2 coaxial nanostructure with Ni wrapping around the TiO2 nanotubes. Moreover, the tube inside was kept empty and tube openings unclogged for the fabricated Ni/TiO2 nanocomposites. Further photodegradation tests using methyl red revealed that the fabricated Ni/TiO2 nanocomposites possess higher photocatalytic efficiency than the counterparts of pristine TiO2 nanotubes. The observed improved photocatalytic efficiency is ascribed to the Schottky barriers formed between Ni and TiO2.