A novel kind of self-assembly polyoxometalate-type hybrid material, [TEAPS] 8 P 2 W 16 V 2 O 62 , bearing of sulfo-group grafted ammonium (TEAPS) and vanadium-substituted heteropoly anions has been prepared. This compound has a layered-shape structure in total and it can process self-assembly to nano-size particle and chrysanthemum-like assemblies through supermolecular interactions. Moreover, from cyclic voltammetry studies, this kind of polyoxometalate-based hybrid compounds exhibit unique electrochemical properties that the vanadium in the complexes can process reduction in anhydrous environment, which is unlikely in water solution as a simple hydrated ion because of the water protonation about the substrate.