In this work, stable and well dispersed colloidal Au/TiO₂ binary nanoparticles (NPs) were synthesized initially. Meanwhile, they were immobilized simultaneously on colloidal carbon spheres (CSs), one of popular hard templates, to prepare hybrid self-assembly nanostructures. The morphology and crystal structure of these nanocomposites (NCs) were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), thermogravimetric (TGA) and N₂ sorption analysis. By controlling the NPs size, ratio of Au/TiO₂ NPs, process temperature and time, and concentration of surfactants (e.g., MPA), Au/TiO₂ @CSs NCs could be tailored into core-shell nanostructures with various surface coverages of Au NPs and/or TiO₂ NPs. Interestingly, hollow spheres with a binary-nanoparticle monoshell could be achieved by calcinations of typical Au/TiO₂ @CSs NCs. In principle, these novel hybrid nanostructures with controllable functionality and high-surface-area traits could be very promising photocatalysts for waste water treatment.