Two novel polyoxotungstates {(H2Biim)2}［SiW12O40］·8H2O (1) and {Ni2(Biim)5}［SiW12O40］·4H2O (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 (H2Biim)2+ as counter cation, while compound 2 belongs to the monoclinic system, with dual-core ［Ni2(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, FTIR, 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 1 050～700 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 Oμ→W(LMCT) of the two compounds was in 254 and 251 nm respectively.