Five new organic-inorganic hybrid compounds based on [P2W18O62]6- (abbreviated as {P2W18}) and several types of transition metal complexes (TMCs) have been synthesized and characterized by IR, UV-Vis, XRD, cyclic voltammetry measurements and single crystal X-ray diffraction analysis. [Cu(phen)2][Cu(phen)(H2O)3][Cu(phen)2(H2O)][P2W18O62]·8H2O (1) (phen = 1,10-phenanthroline) is a {P2W18} bi-supported complex of phen, while [Cu(2,2'-bpy)(H2O)2]2[Cu(2,2'-bpy)2][P2W18O62]·3.5H2O (2) (2,2'-bpy = 2,2'-bipyridine) is a 1-D chain structure formed by {P2W18} and copper complexes of 2,2'-bpy. [Ag(2,2'-bpy)2]5[HP2W18O62]·H2O (3), [Ag(2,2'-bpy)(H2O)]2[Ag(2,2'-bpy)]2[Ag2(2,2'-bpy)3][P2W18O62] (4), and [Ag(2,2'-bpy)(H2O)]3[Ag2(2,2'-bpy)3][Ag(2,2'-bpy)][P2W18O62]·H2O (5) are constructed from {P2W18} and silver complexes of 2,2'-bpy. Compounds 4 and 5 are novel dimers of {P2W18} joined by silver complexes, while compound 3 contains two different kinds of silver complexes, forming a novel supramolecular structure. Each of the five compounds is formed by {P2W18} and more than one type of TMC. The formation mechanism of these compounds has been carefully discussed. In addition, we also synthesized two supramolecular structures based on {P2W18} and organic moieties: [H6P2W18O62](phen)5.5 (6) and [H6P2W18O62](phen)3·43H2O (7). The catalytic properties of these compounds were also tested.