Uniform hollow Au@TiO2 core shell spheres with moveable Au nanoparticles were synthesized based on templating against Au@carbon spheres. The diameter of the shell of the Au@TiO2 spheres could be controlled by adjusting the Ti(OC4H9)4 hydrolyzing reaction time or the ratio of Ti(OC4H9)4 to Au@carbon spheres, and the shell thickness of the core-shell spheres can be varied from 25 nm to 40 nm. As prepared hollow Au@TiO2 core-shell spheres display enhanced photocatalytic activity in the initial stage of photocatalytic degradation of methylene blue compared with pure hollow TiO2 spheres and the commercial photocatalyst TiO2(P-25).