Two new compounds were obtained by modifying hexavanadate cores with pentaerythritol in aqueous solution, however, re-crystallized in water and acetonitrile, respectively. The molecular structures for (Bu4N)(2)[V6O13{(OCH2)(3)CCH2OH}(2)center dot H2O] (1) and (Bu4N)(2)[V6O13{(OCH2)(3)CCH2OH)(2)center dot 4CH(3)CN] (2) (Bu, n-butyl) have been characterized by FT-IR, UV-Vis, and single crystal X-ray diffraction. Compound 1 and 2 crystallize in monoclinic and triclinic space groups, respectively. Compound 1 shows supramolecular chirality in two-dimensional molecular assemblies while 2 does not have such chiral structure. The role of solvent molecules to the formation of supramolecular chirality in self-assembly architectures of polyoxometalates-based hybrid materials is discussed based on these two crystal structures.