The association of metallic clusters (CLUS) and polyoxometalates (POM) into hierarchical architectures is achieved using gamma-cyclodextrin (gamma-CD) as a supramolecular connector. The new self-assembled systems, so-called CLUSPOM, are formed from Dawson-type polyoxometalate [P2W18O62](6-) and electron-rich rhenium clusters. It is worth noting that a cluster-based cation [{Re6Se8}(H2O)(6)](2+) on one hand and a cluster-based anion on the other hand [{Re6Se8}(CN)(6)](4-) can be associated with the anionic POM. In the absence of the supramolecular connector, a "CLUSPOM salt" was obtained from aqueous solution of the cationic cluster and the polyoxometalate. In this solid, the arrangement between the polymetallic building blocks is mainly governed by long-range Coulombic interactions. In the presence of gamma-CD, the Dawson anion and the cationic cluster are assembled differently, forming a hierarchical supramolecular solid, K-2[{Re6Se8}(H2O)(6)](2){[P2W18O62]@2 gamma-CD}center dot 42H(2)O, where the organic macrocycle acts as a ditopic linker between the inorganic building blocks. In such an edifice, the short-range molecular recognition dominates the long-range Coulombic interactions leading to a specific three-dimensional organization. Interestingly, the assembling of anionic POM [P2W18O62](6-) with the anionic rhenium cluster [{Re6Se8}(CN)(6)](4-) is also achieved with gamma-CD despite the repulsive forces between the nanosized anions. The resulting solid, K-10{[{Re6Se8}(CN)(6)]@2 gamma-CD}[P2W18O62]center dot 33H(2)O, is built from 1:2 inclusion complexes {[{Re6Se8}(CN)(6)]@2 gamma-CD}(4-) linked by a POM unit interacting with the exterior wall of the organic macrocycle. Multinuclear NMR and small-angle X-ray scattering investigations support supramolecular preorganization in aqueous solution prior to crystallization.