Designing Hyperbranched Polymers: Core‐Molecule Perspective on Synthesis and Future Challenges

Hyperbranched polymers (HBPs) are a class of 3D macromolecules with a high density of terminal functional groups and are synthetically more accessible than dendrimers. HBPs exhibit low intrinsic viscosity, enhanced reactivity, high solubility, improved thermal stability, tunable mechanical properties, and applications spanning from biomedical to electronic domains. Among the various reported strategies for HBP synthesis, the step‐growth method involving the slow addition of monomers to a multifunctional core molecule enables improved control over their broad molecular weight distribution. This review critically analyses the different HBP synthesis methodologies reported over the last few decades, with particular emphasis on providing the first systematic framework for core‐monomer matching and reaction condition optimization in HBP synthesis, together with their influence on branching behavior, structure–property relationships, and future challenges. This review provides practical guidelines for researchers working on HBP synthesis, including the optimization of reaction conditions for the synthesis of aliphatic and aromatic HBPs, as well as the selection of key analytical techniques for their characterization and application studies.