Sustainability has been a driving factor in the recent development of protective coating systems, from reducing volatile organic compounds (VOC’s), integrating biomass for the replacement of petrochemicals, to reducing the number of synthetic or processing steps within a coating system. Incorporating changes to established technologies requires research initiatives focused on matching or exceeding performance properties while maintaining or lowering costs. As a result, sustainable changes to protective coating systems have been under heavy investigation as market demands shift from petrochemicals to renewable materials. This research focuses on the development of unique thermoset coating systems and sustainable improvements. The first study explores the hydrolytic stability between a silanol and an isocyanate, a frequently used reaction that has been relatively understudied. Incorporation of potential hydrolytically unstable silyl carbamates into polyurethane systems may decrease the crosslinking efficiency of the overall network, negatively impacting coating performance. As a result, investigation into the stability of silyl-carbamates may prevent further inefficiencies by eliminating use of this chemistry within polyurethane systems. The second study focuses on the development of alkoxysilane sol-gel consolidants for the protection of stone materials. Sustainable approaches to consolidant formulation include the reduction and elimination of solvent while improving consolidating properties through material selection. The last two studies focus on the incorporation of lignin-derived vanillin into epoxy thermosets and melamine formaldehydes, increasing the overall biobased content of each system.