Introduction of versatility in materials promotes complex applications, extends their lifespan, and enhances circularity. Additionally, designing materials with their end-of-life in mind is crucial for improving reusability and sustainability. Installing ketones into a polymer backbone is a known method for affecting material properties, like melting temperature and wettability, and introducing photodegradability into polymers, a promising method to lower plastic persistence in the environment; however, most current methods are limited to ethylene–carbon monoxide copolymerization and have restrictions in the polymer architecture and composition. Isocyanides are a provocative isoelectronic alternative for installing functionality to inert polymers through copolymerization with existing commodity monomers. Non-alternating poly(isocyanide-co-acrylate) copolymers enable access to novel polymer microstructures, including the elusive polyketone, with versatile chemistry and allow for designed mechanical properties, an important facet of combating the plastic waste crisis.The contents of this thesis detail the synthesis of non-alternating copolymers of isocyanides, the characterization of these novel materials and their properties, and explores interesting and useful transformations that are possible for these materials. Chapter 1 describes our perspective on the utility of designing materials with their post-consumer lifetime in mind. Polyketones are purposefully described due to the difficulty in synthesis but useful photodegradation properties. Chapter 2 details our foray into using isocyanides to expand the utility of existing materials through radical copolymerization with acrylates and our exploration of the effect on material properties we saw early on. Chapter 3 extends this work, describing the development of a complementary polymerization protocol for isocyanides and furthering the transformations that occur with these novel polymers to access obscure polymer classes. Finally, Chapter 4 details the development of multi-isocyanides as cross-linking monomers capable of directly integrating a dynamic covalent network into polyacrylate backbones resulting in vitrimers, a class of cross-linked polymers that exhibit recyclable characteristics as sustainable alternatives to thermosets due to their dynamic bonds.