An Ag@TiO₂-TiO₂ flower composite is used as a photoanode in a photoelectrochemical cell. The photoanode shows exceptional performance in the simultaneous photodegradation of organic compounds and photogeneration of electrical power. The TiO₂ flower composite provides a hierarchical morphology that greatly improves the electronic properties of the anode. The addition of small quantities of Ag@TiO₂ immediately improves the short-circuit current of a methanol photocatalytic fuel cell, and the optimal addition of Ag@TiO₂ enhances the maximum power output of the cell under solar simulated light. Compared to commercial TiO₂ material, the Ag@TiO₂-TiO₂ flower composite improves the short-circuit current of the photocatalytic fuel cell by 97% (1.7 mA cm^-2) and the maximum power by 131% (0.6 mW cm^-2) under solar simulated light.