A general route to organic-inorganic hybrids with nanophase morphologies has been elaborated with the objective of ultimately generating nanoporosity in organosilicates. Hyperbranched block copolymers prepared by either the sequential or concurrent polymerization of an ABC monomer (I3-(Im-caprolactone) 2-bromo-2-dimethylpropionate) with a BCD monomer (2-hydroxyethyl methacrylate) were used as the macromolecular templates. The two monomers, each polymerizing by different chemistries, for example ring-opening polymerization and atom transfer radical polymerization, bear initiating centres that are targeted for the functionality located on the accompanying monomer. Consequentially, a branched polymer is obtained which avoids the traditional multistep procedures. The branching density was altered simply by the addition of the appropriate AB (Im-caprolactone) and/or CD (methyl methacrylate) comonomers. These polymers were readily soluble initially in the organosilicate prepolymer (methyl silsesquioxane).