The　first　two　tetra-Sc-substituted　polyoxotungstates　H2K2Na2[Sc-4(H2O)(10)(B-beta-SbW9O33)(2)]center　dot　21H(2)O　(1)　and　H20K2Na6[Sc-4(C2O4)(4)(B-beta-SbW9O33)(2)][Sc-4(H2O)(2)(C2O4)(4)(B-beta-SbW9O33)(2)]center　dot　64H(2)O　(2)　have　been　synthesized　and　characterized　by　IR　spectroscopy,　AC　impedance　measurements,　TG,　PXRD,　and　single-crystal　X-ray　diffractions.　Compound　1　represents　an　isolated　inorganic　sandwich-type　dimeric　POM　constructed　from　two　trilacunary　Keggin　[B-beta-SbW9O33](9-)　moieties　and　four　Sc3+　ions,　while　compound　2　shows　an　extended　organic-inorganic　hybrid　POM　which　composes　of　two　kinds　of　distinct　tetra-Sc-substituted　polyoxotungstate　building　units　and　oxalate　ligands.　Notably,　these　two　compounds　also　are　the　first　Sc-containing　polyoxotungstates　based　on　trilacunary　Keggin　[B-beta-SbW9O33](9-)　clusters.　Electrochemical　study　showed　that　compound　2　has　good　proton　conductivity.　(C)　2017　Elsevier　B.V.　All　rights　reserved.