The fabrication of well-ordered arrays of well-defined nanoparticles or clusters is of fundamental and technological interest. As this is a difficult task, different techniques have been employed.1 An elegant approach would be to link well-defined building blocks in a chemically straightforward procedure yielding a monodisperse or a completely homogeneous material. We succeeded now to cross-link assembled nanosized metal-oxide-based clusters/composites – novel supramolecular entities – under one-pot conditions. Pertinent targets include the synthesis of materials with network structures that have desirable and predictable properties, such as mesoporosity2 (due to well-defined cavities and channels), electronic and ionic transport,3 ferro- as well as ferrielasticity, luminescence and catalytic activity.4 The synthesis of solids from pre-organized linkable building blocks with well-defined geometries and chemical properties is, therefore, of special interest.5 In this article, we will focus on the relationship between some polyoxomolybdate-based wheel- and ball-shaped clusters and network structures derived from these precursors.6 Accordingly, a strategy will be presented that allows the intentional synthesis of solid-state materials, both by designing and utilizing known clusters that can be treated as synthonbased building blocks (and thus these synthons can be linked together), with preferred structure and function