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This dissertation covers the development of redox-switchable ring-opening polymerizations for the synthesis of copolymers of underutilized monomers. In Chapter one, the progress in the development of switchable methods for ring-opening polymerization and ring-opening copolymerizations. Chapter two describes a method for the redox-switchable copolymerization of L-lactide, propylene oxide and carbon dioxide. The benefits of this method are demonstrated through the facile synthesis of blocky and statistical copolymers of the three monomers. In Chapter three, a method for the redox-switchable polymerization of N-carboxyanhydrides is presented. A mechanistic analysis and copolymerizations of N-carboxyanhydrides and either lactones or epoxides follow the initial findings. Chapter four further expands the uses of N-carboxyanhydride redox-switchable polymerizations by immobilizing the catalysts onto semiconductor surfaces for the synthesis of surface bound polyamides.