Through the use of a strategy that involves narrowing the TiO2 band gap by shifting its conduction band positively and utilizing the catalytic activity of photoproduced Cu(I) for oxygen reduction, a novel visible-light-sensitive TiO2 photocatalyst, Cu(II)-grafted Ti1-3xWxGa2xO2, was designed and synthesized. The Cu(II)/Ti1-3xWxGa2xO2 photocatalyst produced high activity under visible-light irradiation. In fact, it decomposed 2-propanol to CO2 via acetone under visible light (>400 nm) with a high quantum efficiency of 13%. The turnover number for this reaction exceeded 22, indicating that it functioned catalytically.