This article describes an account of some of our polyoxometalate (POM)-based research, we have been doing in our laboratory last several years. There are several well-defined POM cluster anions, that are structurally characterized. We have chosen Anderson-type of heteropolyanion [Al(OH)6Mo6O18]3- and explored its linking propensity in different dimensions using 's', 'd' and 'f' block elements as linkers.We have demonstrated how a lanthanide linker provides a new pathway in forming a two-dimensional linked {As8V14} system [{Ln(H2O)6}2As8V14O42(SO3)]n · 8nH2O, that is derived from discrete {As8V14} cluster containing compound (NH4)6[As8V14O42(SO3)]. A polyoxometalate compound has been described in which a reduced tungstovanadate-heteropolyanion clusters get linked via capped V = O groups into one-dimensional chains. All these systems have already been reported elsewhere. The last portion of this article will be described by a new system [3-ampH]6[V10O28] · 2H2O having discrete molecular structure and extended supramolecular structure
