Abstract: The system provides new methods and processes for the reaction of polymeric/oligomeric substrates with reactants comprising alkyne/alkene and/or protic nucleophilic moieties to afford functionalized polymeric/oligomeric products through the utilization of homogenous and/or heterogenous gold catalysis. More specifically, the system provides routes for reaction of polymeric/oligomeric substrates comprising varying degrees of aromatic character with alkyne/alkene bearing molecules to afford a functionalized polymeric/oligomeric product. The system additionally provides pathways wherein the inverse methodology is realized, providing functionalized materials from the reaction of polymeric substrates bearing alkyne/alkene moieties with aromatic and/or protic nucleophilic reagents. Furthermore, in a tangential methodology, the system affords functionalized polymeric materials from the reaction of polymeric substrates bearing protic nucleophilic substituents with alkyne/alkene containing molecules.