A　facile　one-pot　pH-dependent　hydrothermal　method　has　been　developed　in　the　controlled　syntheses　of　CaSb2O5(OH)(2)　and　cubic　Ca2Sb2O7　with　large　specific　surface　area.　The　as-obtained　samples　were　characterized　by　X-ray　diffraction　(XRD),　N-2-sorption　BET　surface　area,　UV-vis　diffuse　reflectance　spectroscopy　(DRS),　transmission　electron　microscopy　(TEM),　high-resolution　transmission　electron　microscopy　(HRTEM),　energy　dispersive　X-ray　analysis　(EDX)　and　Fourier　transformation　infrared　spectroscopy　(FT-IR).　The　electronic　structures　of　CaSb2O5(OH)(2)　and　cubic　Ca2Sb2O7　were　determined　by　density　functional　theory　(OFT)　calculations.　The　photocatalytic　performance　of　the　as-prepared　CaSb2O5(OH)(2)　and　cubic　Ca2Sb2O7　was　evaluated　by　the　degradation　of　methyl　orange　(MO)　and　gaseous　benzene.　It　was　found　that　CaSb2O5(OH)(2)　is　more　photocatalytic　active　than　Ca2Sb2O7.　A　low　crystal　packing　factor　(PF)　of　CaSb2O5(OH)(2)　is　probably　responsible　for　its　superior　photocatalytic　performance　as　compared　to　that　of　cubic　Ca2Sb2O7.　(C)　2012　Elsevier　B.V.　All　rights　reserved.