AbstractIn this study, ester‐protected vinyl catechols (VCs) derived from caffeic acid are synthesized to design novel functional copolymers. The protected VCs are polymerized or copolymerized with a series of common vinyl monomers via reversible addition‐fragmentation chain transfer (RAFT) polymerization using cumyl dithiobenzoate as the RAFT agent. The RAFT polymerizations of these protected VCs have been successfully proceeded to afford well‐defined polymers with relatively narrow molecular weight distributions. The deprotection of catechol ester proceeded quantitatively and selectively by primary amine with the formation of amide under a mild condition. In particular, the random/statistical and block copolymerization led to catechol‐containing copolymers with well‐defined structures.