Transforming biomass derived components to materials with controlled and predictable properties is a major challenge. Current work describes the controlled synthesis of starcopolymers with functional and degradable arms from the Lignoboost® process. Macromolecular control is achieved by combining lignin fractionation and characterization with ring-opening copolymerization (ROCP). The cyclic monomers used are ε-caprolactone (εCL) and a functional carbonate monomer, 2-allyloxymethyl-2-ethyltrimethylene carbonate (AOMEC). The synthesis is performed at ambient temperature, under bulk conditions, in an open flask, and the graft composition and allyl functionality distribution are controlled by the copolymerization kinetics. Emphasis is placed on understanding the initiation efficiency, structural changes to the lignin backbone and the final macromolecular architecture. The present approach provides a green, scalable and cost effective protocol to create well-defined functional macromolecules from technical lignins.