It　is　indispensable　to　find　a　suitable　preparation　method　to　optimize　the　photocatalyst　performance.　Different　ZnSn(OH)6　(ZHS)　were　prepared　by　four　methods　in　this　report,　including　grinding,　co-precipitation,　self-templating,　and　hydrothermal　processes.　The　crystal　structures,　optical　properties,　thermal　stabilities,　and　morphologies　of　the　ZHS　samples　were　investigated　systematically.　Photocatalytic　degradation　of　methyl　orange　(MO)　and　gaseous　benzene　(C6H6)　over　the　samples　were　assessed　and　compared.　The　relationship　between　the　microstructure　and　the　photocatalytic　performance　of　ZHS　was　analyzed.　The　results　reveal　the　surface　microstructure　and　the　photocatalytic　performance　of　ZHS　are　more　sensitive　to　the　preparation　methods　than　the　crystal　structure　and　the　morphology.　A　harsh　preparation　condition　leads　to　the　formation　of　some　OH-unsaturated　Zn　and　Sn　atoms　due　to　the　susceptible　of　OH　groups,　which　result　in　a　tail　light　absorption　of　ZHS　and　are　assumed　as　the　photoactive　center.　ZHS　prepared　by　the　PVP-assisted　hydrothermal　method　exhibits　the　highest　thermal　stability,　optical　absorption,　BET　surface　area　and　ability　for　O2　activation,　and　consequently　shows　the　highest　photocatalytic　activity　and　stability　for　the　degradation　of　MO　and　gaseous　C6H6.　©　2013　Elsevier　B.V.