Azlactone-based homopolymers and copolymers were successfully synthesized using the reversible additionfragmentation chain transfer (RAFT) process. The functional monomer 2-styryl-4,4-dimethylazlactone (SDA) was first homopolymerized in bulk then copolymerized with styrene, leading to (co)polymers with low polydispersity indices (PDI = 1.101.20). The reactive azlactone rings, located along the backbone of the copolymers were subjected to highly efficient ring-opening reactions with functionalized primary amine derivatives incorporating a fluorescent (naphthalene) or an electrochemical (ferrocene) probes, a biological fragment (glutathione), a sugar unit (beta-cyclodextrin), or an oligomeric fluorinated moiety, leading to materials with various interesting properties.