Abstract: The present invention describes preparation of nanocomposite particles and structures by polymerizing monomers onto a functional inorganic colloid comprising a polymerization initiation site. The polymerization process is preferably a controlled/living polymerization process, including but not limited to, atom transfer radical polymerization and stable free radical polymerization. The nanocomposite particles can self-organize in solution, on surfaces or in films forming nanocomposite structures. Tethered AB block nanocomposite particles bring size control, solubility control and control over micro- and macro-functionality to the particles. The process may be catalyzed by a transition metal complex which participates in a reversible redox cycle with at least one of the group and a compound having a radically transferable atom or group, to form a nanocomposite particle with a tethered polymer chain. The process may be continued to form tethered copolymer chain.