Yolk@shell nanostructures of Au@r-GO/TiO2, with mesoporous shells were prepared by a sol-gel coating process sequentially with GO and TiO2 on Au/SiO2 core/Shell spheres, followed by calcination and template removal, where the silica interlayer acts as a template not only to produce the void space but also to promote the coating of the r-GO and TiO2 layer. The evaluation of visible light photo catalytic activities in dye decomposition and water-splitting H-2 production demonstrated their superior photocatalytic performance, which indicates their potential as powerful photocatalysts.