We　report　the　synthesis　of　TiO2/ZnSn(OH)6　as　a　novel　nano-composite　material　via　a　simultaneous　crystallization-etching　route　with　cubic　nano-ZnSn(OH)6　and　TiF4　as　the　precursors.　The　structure,　composition　and　morphology　of　the　composite　were　characterized　by　XRD,　EDS,　FETEM　and　FESEM,　which　showed　the　prepared　TiO2/ZnSn(OH)　6　had　a　unique　morphology　of　hollow　cubic　nano-ZnSn(OH)6　attached　with　rutile　TiO2　nanoparticles.　The　results　of　photocatalytic　activity　measurement　indicated　the　photocatalytic　activity　of　the　prepared　composite　was　better　than　that　of　nano-ZnSn(OH)6.　This　study　may　be　helpful　for　the　design　and　fabrication　of　functional　composite　materials.　Copyright　©　2013　Editorial　Board　of　Chinese　Journal　Of　Structurnal　Chemistry.