Bi　2　WO　6　hollow　microspheres　with　dimension　of　ca.　1.5　μm　were　synthesized　via　a　hydrothermal　method　using　polystyrene　particles　as　the　template.　The　as-prepared　Bi　2　WO　6　hollow　microspheres　can　be　further　transformed　to　double-shell　Bi　2　O　3　/Bi　2　WO　6　hollow　microspheres.　The　samples　were　fully　characterized　by　X-ray　diffraction,　scanning　electron　microscopy,　transmission　electron　microscopy　(TEM),　high-resolution　TEM,　N　2　-sorption　Brunauer-Emmett-Teller　surface　area,　UV-vis　diffuse-reflectance　spectroscopy,　and　X-ray　photoelectron　spectroscopy.　The　as-formed　double-shell　Bi　2　O　3　/Bi　2　WO　6　hollow　microspheres　exhibit　enhanced　photocatalytic　activity　due　to　the　hollow　nature　and　formation　of　the　p-n　junction　between　p-type　Bi　2　O　3　and　n-type　Bi　2　WO　6　.　The　study　provides　a　general　and　effective　method　in　the　fabrication　of　composition　and　dimension-tunable　composite　hollow　microspheres　with　sound　heterojunctions　that　may　show　a　variety　of　applications.　©　2012　American　Chemical　Society.