Nanocrystalline　ZnSb2O6　with　small　particles　size　and　large　BET　specific　area　(131.4　m2/g)　was　successfully　prepared　via　a　facile　hydrothermal　method　directly　from　Sb2O5　and　was　fully　characterized　by　X-ray　diffraction　(XRD),　N2-sorption　BET　surface　area,　UV-vis　diffuse　reflectance　spectroscopy　(DRS),　scanning　electron　microscopy　(SEM),　transmission　electron　microscopy　(TEM),　and　high-resolution　transmission　electron　microscopy　(HRTEM).　The　as-prepared　ZnSb2O　6　showed　photocatalytic　activity　for　the　degradation　of　typical　dyes　rhodamine　B　(RhB)　and　methyl　orange　(MO)　in　the　aqueous　solution　under　UV　irradiations.　The　electronic　structure　of　ZnSb2O6　was　studied　by　density　functional　theory　(DFT).　The　different　photocatalytic　performance　between　ZnSb2O6　and　Sr2Sb　2O7,　another　ternary　antimonate　photocatalyst,　can　be　explained　in　terms　of　their　different　electronic　structures　and　different　crystal　structures.　©　2011　Elsevier　B.V.　All　rights　reserved.