Taking advantage of the structural characteristics of lignin-derived phenolic compounds, a combination of the Williamson and Tishchenko reactions produced a series of new α,ω-diene functionalized carboxylic ester monomers from both petrochemical and renewable resources, which were applicable in subsequent thiol–ene click and acyclic diene metathesis (ADMET) polymerizations, providing a series of poly(thioether esters) and unsaturated aromatic–aliphatic polyesters with high molecular weights.