A　novel　hollow　meso-TiO2/ZnO　composite　microsphere　is　fabricated　by　simple　sol-gel　and　hydrothermal　method,　and　could　be　a　binary　photocatalytic　material.　The　carbon　sphere　is　used　as　the　hollow　template　for　the　composite　material,　then　the　meso-TiO2　used　as　the　inner　shell　and　the　nanometer　ZnO　as　the　outer　shell.　The　results　of　photocatalytic　degradation　for　methyl　orange　show　that　the　photocatalytic　performance　of　the　composite　is　better　than　that　of　a　single　photocatalyst,　degradation　rate　is　up　to　96.9%　after　2.5　h　under　UV　light.　Compared　with　meso-TiO2,　the　excitation　wavelength　of　composite　microspheres　has　moved　12　nm　in　the　direction　of　visible　light.　The　meso-TiO2/ZnO　composite　microsphere　has　higher　photocatalytic　performance,　which　is　attributed　to　the　hollow　structure　and　the　synergy　of　meso-TiO2　and　ZnO.　The　hollow　structure　and　mesoporous　channel　are　used　as　the　storage　warehouse　and　transport　channel　of　methyl　orange　molecule　respectively.　Graphical　Abstract　The　hollow　structure　and　mesoporous　channel　are　used　as　the　storage　warehouse　and　reaction　channel　of　methyl　orange　molecule,　respectively.　The　higher　photocatalytic　performance　of　meso-TiO2/ZnO　composite　microsphere　is　also　attributed　to　the　synergy　of　meso-TiO2　and　ZnO.　[GRAPHICS]　.