In order to harvest the solar energy more efficiently, a novel photocatalyst was designed by introducing an organic dye sensitizer, copper phthalocyanine (CuPc), into an inorganic semiconductor Bi₂WO₆. This composite photocatalyst exhibited an improved photo-response in the whole visible spectrum and even the near infrared region. Under a red LED (λ = 620 nm) irradiation, the CuPc/Bi₂WO₆/FTO electrode showed photocurrent response. The photo-degradation of RhB and phenol under simulated solar light demonstrated that the CuPc–Bi₂WO₆ composite exhibited much higher photocatalytic activity than bare Bi₂WO₆. Moreover, the composite photocatalyst also showed photo-activity under a red LED (λ = 620 nm) irradiation, further testifying the sensitization effect of CuPc. This study provides a new strategy to increase the utilization rate of solar energy substantially.