Lysine, a renewable feedstock with economic feasibility, was tactfully cyclized to its corresponding cyclic lysine and then subjected to a reaction with acetylenes to yield a sustainable N-vinylcaprolactam (VCL) derivative. Subsequent MADIX/RAFT copolymerization of the resultant monomer gave well-defined PVCL bearing pendant 2,5-dimethylpyrrole protected amino groups with narrow polydispersity.