The synthesis and characterization of new highly biodegradable multipropargyl and comb-like copolyurethanes have been successfully achieved by the combination of step-growth polymerization and click chemistry. This work discloses a simple, accurate, and straightforward method to generate brush polymers with an excellent control of the branch nature, distribution, and density in the final materials. The introduction of controlled branching has led to a great variety of polymers, whose hydrophilic/lipophilic characters were adjusted as required. Furthermore, their stiffness, semicrystalline nature, and degradability were fine-tuned by appropriate selection of the monomers and their feed ratios. The presence of propargyl functional groups in the (co)polymers was confirmed by the presence of a thermal degradation step in the range from 450 degrees C to 455 degrees C. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3888-3900