Simultaneous　H2　production　and　benzyl　alcohol　oxidation　is　an　effective　strategy　for　fully　utilizing　photoexcited　electrons　and　holes　of　the　photocatalysts.　Herein,　PtO　are　decorated　on　hollow　CdS　microspheres　to　fabricate　a　coupling　photocatalytic　system　for　accelerating　H2　generation　and　selective　oxidation　of　benzyl　alcohol　to　benzaldehyde.　The　PtO-CdS　hollow　microspheres　have　been　prepared　by　a　facile　hydrothermal　method　without　any　template　agents.　Under　simulated　sunlight　irradiation,　the　1　%PtO/CdS　exhibited　the　highest　rates　of　H2　evolution　and　benzaldehyde　production.　In　addition,　the　PtO-CdS　photoctalyst　is　stable　during　five　cycles　of　photocatalytic　reaction.　Photoelectrochemical　analyses　coupled　with　ESR　measurement　demonstrated　that　PtO　decoration　not　only　promotes　the　charge　separation　but　also　improves　the　stability　of　the　CdS.　It　is　hoped　that　this　work　would　provide　useful　information　for　the　synthesis　of　CdS　nanostructure　for　target　application.