The coupling of controlled polymerizations with orthogonal Click functionalization are critical design elements for the synthesis of well-defined macromolecular architectures and crosslinked networks for applications ranging from bio-adhesives to structural composites. In synthesizing these functional materials, the development of user-friendly approaches to the preparation of polymeric libraries and the discovery of sustainable monomers and building blocks are key to obtaining materials with exceptional properties while introducing desirable features such as degradability.