TiO2/CdS porous hollow microspheres have been one-pot rapidly synthesized by a salt-assisted aerosol decomposition method, and exhibit an excellent photocatalytic activity of 996 μmol h(-1) (50 mg photocatalysts with loading Ru co-catalyst) for hydrogen evolution from aqueous solutions containing sacrificial reagents (SO3(2-) and S(2-)) under visible light (λ ≥ 420 nm). Its high photocatalytic performance is attributed to the surface morphology, crystallinity and heterostructures. The present facile method can be extended to fabricate other heterostructures consisting of oxides or sulfides.