It is crucial to adapt the processing of forest bio-resources into biochemicals and bio-based advanced materials in order to transform the current economic climate into a greener economy. Tall oil, as a by-product of the Kraft process of wood pulp manufacture, is a promising resource for the extraction of various value-added products. Tall oil fatty acids-based multifunctional Michael acceptor acrylates were developed. The suitability of developed acrylates for polymerization with tall oil fatty acids-based Michael donor acetoacetates to form a highly crosslinked polymer material via the Michael addition was investigated. With this novel strategy, valuable chemicals and innovative polymer materials can be produced from tall oil in an entirely new way, making a significant contribution to the development of a forest-based bioeconomy.