Recent advances in the synthesis of block, graft and star polymers containing inorganic macromolecular species are described. Anionic copolymerization techniques were used in the formation of diblock copolymers of poly(styreneblock-methylphenylsilylene) and poly(isopreneblock-methylphenylsilylene) by the ring-opening polymerization of 1,2,3,4-tetramethyl-1,2,3,4tetraphenylcyclotetrasilane initiated by living anionic polystyrene and isoprene respectively. Hydrosilation of an attachable initiator onto telechelic vinyl-or hydrosilyl-terminal or -pendant poly(dimethylsiloxane) (PDMS) yielded a PDMS macroinitiator. This macroinitiator was used in atom transfer radical polymerization (ATRP) of styrene and isobornyl acrylate to produce ABA triblock copolymers. As a model for graft copolymers from a polyphosphazene backbone, chemical transformation of hexachlorocyclotriphosphazene resulted in hexafunctional molecules containing either benzyl bromide or bromopropionyl moieties. The initiator 1,1,3,3,5,5-hexakis[4-(2bromopropionyloxymethyl)phenoxy]cyclotriphosphazene was used in the ATRP of styrene to yield a polymer with a narrow, monomodal molecular weight distribution. Chain extension of this star polymer with isobornyl acrylate is also described.