A straightforward and stepwise functionalization of poly(limonene carbonate) (PLC) was achieved through the use of thiol-ene click chemistry introducing primary amine groups. These amines are initiating points for N-carboxy anhydride (NCA) ring-opening polymerization (ROP) reactions, allowing us to modify the PLC backbone with oligolysine fragments, thereby creating a polymer brush type macromolecule. These newly prepared biohybrid structures show a clear hydrophilic behavior as evident from their physical behavior and contact angle measurements.