We　report　here　a　facile　one-step　strategy　to　prepare　hollow　ZnO　core/ZnS　shell　structures　by　microwave　irradiation.　The　growth　mechanism　of　the　hollow　core/shell　structures　was　investigated　in　detail.　ZnO　truncated　hexagonal　pyramids　first　form　on　as-grown　precursor　flakes　and　then　evolve　into　ZnO　hexagonal　twin　crystals,　which　subsequently　grow　up　and　dissolve　internally.　The　hollowing　progress　is　firstly　controlled　by　the　Kirkendall　effect　and　then　undergoes　an　Ostwald　ripening　process.　Hollow　structures　and　the　formation　of　ZnO/ZnS　heterostructure　bring　enhanced　photocatalytic　activities　to　ZnO　core/ZnS　shell　structures.　The　formed　ZnO/ZnS　heterostructures　also　fill　the　surface　defects　of　ZnO　crystals　and　improve　the　stability　of　the　photocatalysts　by　overcoming　the　photocorrosion　effect　of　a　single　ZnO　photocatalyst　under　UV　light　irradiation.　Superoxide　radicals　(O-2(center　dot-))　are　the　key　active　species　in　the　photocatalytic　system　of　degradation　of　p-chlorophenol　over　hollow　ZnO　core/ZnS　shell　structures.　The　photocatalysis　process　has　been　discussed　and　a　possible　mechanism　also　has　been　proposed.　This　work　is　helpful　to　controllably　construct　other　hollow　core/shell　structures,　develop　ZnO-based　photocatalysts　without　photocorrosion　effect　and　further　study　the　photocatalytic　mechanism　of　similar　systems.