Two Bi (III) contained heteropolymate compounds Cos [Bi2 Co2 W20 O70 (H2O)6] x 44H2O (I)and Na3 H2 [Ce3 (H2O)18 Bi2 W22 O76] x 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 nu(as) (M = O(d)) and nu(s) (M-O(b)-M) is related to the structure of the materials. Nu(as) (M-O(b)-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 coresponding O(d) --> W and to O(b), 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.