In this work, TiO2 nanoparticles/Cu nanowires (TiO(2)NPs@CuNWs) binary composites with tunable coverage of TiO2 nanoparticles were prepared by a facile method of mixing oleic acid-modified TiO2 nanoparticles with as-prepared Cu nanowires. Characterization studies including X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and high-resolution transmission electron microscopy were applied to investigate the structure and morphology of the as-synthesized TiO(2)NPs@CuNWs binary composites. The photocatalytic activity of TiO(2)NPs@CuNWs binary composites was examined by photodegradation of methyl orange. The enhanced photocatalytic efficiency of TiO(2)NPs@CuNWs nanocomposites was ascribed to the moderate specific surface area, mesoporous structures, and the electron sink effect of the Cu nanowires. In principle, our investigation indicates that the TiO2@Cu self-assembled nanostructures can be a promising candidate of composite photocatalysts.