Two　Bi(III)　contained　heteropolymate　compounds　Co5[Bi2Co2　W20O70(H2O)6]　·44H2O(I)　and　Na3H2　[Ce3(H2O)18　Bi2W22O76]　·23H2O(II)　have　been　synthesized　under　hydrothermal　condition.　The　relationship　between　their　properties　and　structures　was　studied　by　using　FTIR,　NIR　FT-Raman,　and　UV-Vis　DRS　etc.　The　characteristic　vibrational　frequencies　vas　(M=Od)　and　vs(M-Ob-M)　is　related　to　the　structure　of　the　materials.　vas(M-OB-M)　is　demonstrated　to　explain　why　the　the　oxidative　ability　becomes　stronger　when　W　atoms　are　substituted　by　Co　atoms.　In　UV-Vis　DRS　spectra　of　compound　I　and　II,　there　are　two　characteristic　peaks　at　254,　319　nm　and　220,　310　nm　corresponding　Od→W　and　to　Ob,　c→W　charge　transfer,　respectively.　The　wide　and　weak　absorption　band　of　compound　I　at　529　nm　can　be　assigned　as　Co2+　d-d　transfer.　Finally,　quantum　chemistry　calculation　of　compound　I　was　performed　to　explain　the　structure　characteristic.