The　controlled　synthesis　of　ZnO　hollow　spheres　is　successfully　achieved　through　a　facile　solvothermal　method　using　a　Keggin-type　silicotungstic　acid　(H4Si(W3O10)(4):HSW)　as　structure　directing　agent.　The　formation　process　of　these　hollow　spheres　is　proposed　based　on　a　variety　of　controlled　experiments.　In　addition,　Au　nanoparticles　are　loaded　onto　the　surface　of　ZnO　hollow　spheres.　It　is　found　that　the　Au-loaded　ZnO　(Au/ZnO)　composites　exhibit　greatly　enhanced　activity　on　oxidizing　Rhodamine　B　(RhB)　under　simulated　UV　or　visible　light　irradiation,　compared　to　the　pristine　ZnO　hollow　spheres.　The　improved　performance　of　Au/ZnO　heterostructures　is　mainly　attributed　to　the　enhanced　optical　absorption　and　the　accelerated　separation　and　migration　of　photogenerated　charge　carriers.　Moreover,　the　photocatalytic　reaction　mechanisms　are　proposed　based　on　the　results　of　electron　spin　resonance　(ESR)　analysis,　photoelectrochemical　measurements,　and　photocatalytic　evaluation.　The　results　and　findings　are　expected　to　provide　significance　to　the　synthesis　of　noble　metal-semiconductor　hybrids　towards　water　purification.