Two　novel　polyoxotungstates　{(H(2)Biim)(2)}　[SiW(12)O(40]center　dot)8H(2)O　(1)　and　{Ni-2　(Biim)(5)}　[SiW12O40]center　dot　4H(2)O　(2)　have　been　hydrothermally　synthesized.　The　two　compounds　are　formed　by　classic　Keggin　configuration　cluster　anions　as　building　blocks.　The　compound　1　belongs　to　the　tetragonal　system　with　protonated　(H-2　Biim)(2+)　as　counter　cation,　while　compound　2　belongs　to　the　monoclinic　system,　with　dual-core　[Ni-2　(Biim)(5)](4+)　complex　as　a　counter　cation　of　which　the　Ni2+　ion　is　five-coordinated.　The　relationship　between　their　properties　and　structures　were　studied　by　using　XRD,　FI　IR,　two-dimensional　(2D)　correlation　infrared　spectroscopy　under　thermal　perturbation,　and　Uv-Vis　DRS　spectrum　ect.　Infrared　spectra　showed　that　the　stretching　vibration　of　Keggin　cluster　anion　skeleton　appeared　in　the　range　of　1　050　similar　to　700　cm(-1),　furthermore　the　two-dimensional　infrared　correlation　spectroscopy　illustrated　that　the　anion　cluster　skeleton　is　very　sensitive　with　the　thermal　response;　UV-Vis　DRS　found　the　O-mu　-＞　W(LMCT)　of　the　two　compounds　was　in　254　and　251　nm　respectively.