A　novel　Zr-substituted　polyoxometalate　(POM)　H2K3[Na-6(H2O)(9)][Zr3Na3O3(H2O)(3)-(GeW9O34)(2)]center　dot　12H(2)O　(1)　has　been　made　under　hydrothermal　conditions.　1　was　characterized　by　infrared　spectrum,　thermogravimetric　analysis,　powder　X-ray　diffraction　and　single-crystal　X-ray　diffraction.　Crystal　data　are:　H50O95Na9K3Ge2Zr3W(1)(8),　hexagonal　space　group　P6(3)/mmc,　a　=　15.2251(6),　b　=　15.2251(6),　c　=　25.035(2)　angstrom,　V　=　5025.7(6)　angstrom(3),　Z　=　2,　D-c　=　3.716　mg/m(3),　mu　=　21.648　mm(-1),　F(000)　=　4726,　the　final　R　=　0.0259　and　wR　=　0.0647　for　1487　observed　reflections　with　I　＞　2　sigma(I).　Single-crystal　X-ray　structure　analysis　reveals　that　1　exhibits　a　3-dimensional　framework　structure　based　on　Zr3Na3-substituted　polyanions　[Zr3Na3O3(H2O)3(GeW9O34)(2)](11-)　and　[Na-6(H2O)(9)](6+)　clusters　building　blocks.　UV-Vis　spectrum　indicates　that　1　is　a　wide-gap　semiconductor.　In　addition,　the　proton-conducting　property　of　1　was　also　investigated.