The design and utility of a family of isocyanate functionalized branched monomers, as well as others, are described. Use of these monomers in logical combinations for the construction of branched architectures leads to the formation of unique, asymmetric dendritic species possessing multiple functionalities. Ramifications of this combinatorial-based, macromolecular construction technique are discussed with respect to functional group positioning and the potential to create dynamic heterogenous surfaces resembling a molecular "Rubik's sphere."