This article describes hybrid materials and systems in which the core integrity of inorganic nanobuilding blocks (NBBs) is preserved and reviews the main synthetic procedures presented in the literature. The relation between the NBB and the resulting hybrid networks is discussed for several striking examples:  silicon and tin oxo clusters, polyoxometalates, and transition metal−oxo-based clusters. This approach is extended to nanoparticule-based hybrids. The chemical strategies offered by the coupling of soft chemistry processes and this approach based on functional NBBs allows, through an intelligent and tuned coding, to develop a new vectorial chemistry that is able to direct the assembly of a large variety of structurally well-defined clusters or nanoparticles into complex architectures.

Contents 1. Introduction 6009 2. Organic Groups Covalently Linked to Polyoxometalate Units via p-Block Elements 6011 2.1. Presentation and Generalities on the Functionalization of POMs 6011 2.1.1. Importance of the Anchorage Point 6011 2.1.2. Nature, Degree, and Localization of the Functionalization 6011 2.1.3. Influence of the Nature of the POM 6012 2.