A novel metal/semiconductor hybrid nanostructure with enhanced catalytic functions has been prepared by a simple self-assembly approach. This new bifunctional nanocatalyst consists of evenly dispersed Au/Pt hybrid nanoparticles (Au/Pt NPs) assembled on NH2 group functionalized anatase TiO2 colloid spheres with nanoporous surface (f-TiO2). The resulting bimetallic nanoparticles/TiO2 (noted as f-TiO2-Au/Pt NPs) hybrid nanostructure is characterized by various methods and expected as a promising catalyst in electrochemical and photoelectrochemical applications because of its satisfactory or even enhanced catalytic properties from both TiO2 and Au/Pt NPs. Compared with the f-TiO2, the electrochemical results indicate that the as-prepared f-TiO2-Au/Pt NPs exhibited more prominent electrocatalytic reduction toward hydrogen peroxide at low potential, which was then used as a sensitive sensor with a detection limit of 75 nM. Most importantly, the present hybrid material has the better photocatalytic property, as demonstrated by the photoelectrochemical catalysis of glucose.