Hyperbranched polymers (HPs) are highly branched three-dimensional (3D) macromolecules. Their globular and dendritic architectures endow them with unique structures and properties such as abundant functional groups, intramolecular cavities, low viscosity, and high solubility. HPs can be facilely synthesized via a one-pot polymerization of traditional small molecular monomers or emerging macromonomers. The great development in synthetic strategies, from click polymerization (i.e., copper-catalyzed azide–alkyne cycloaddition, metal-free azide–alkyne cycloaddition, strain-promoted azide–alkyne cycloaddition, thiol–ene/yne addition, Diels–Alder cycloaddition, Menschutkin reaction, and aza-Michael addition) to recently reported multicomponent reactions, gives rise to diverse HPs with desirable functional/hetero-functional groups and topologies such as segmented or sequential ones. Benefiting from tailorable structures and correspondingly special properties, the achieved HPs have been widely applied in various fields such as light-emitting materials, nanoscience and technology, supramolecular chemistry, biomaterials, hybrid materials and composites, coatings, adhesives, and modifiers. In this review, we mainly focus on the progress in the structural control, synthesis, functionalization, and potential applications of both conventional and segmented HPs reported over the last decade.

A new kind of segmented hyperbranched polymers (SHPs), hyperbranched poly(glycidyl methacrylate)s (HPGMAs), were synthesized via reversible addition–fragmentation chain transfer self-condensing vinyl polymerization (RAFT-SCVP). HPGMAs were efficiently functionalized on the whole scaffold via a collection of click chemistries, including the azidation of oxirane, thiol–epoxy click chemistry, thiol–ene click chemistry, copper-catalyzed azide–alkyne cycloaddition (CuAAC), and Menschutkin chemistry, affording SHPs with hetero-functional groups including hydroxyl + azide, dual hydroxyl, triple hydroxyl, hydroxyl + tertiary amine, hydroxyl + alkene, hydroxyl + carboxyl, alkene + azide, alkyne + azide, hydroxyl + alkyne, dual hydroxyl + alkene etc., all at ∼100% conversion. “Thiol–epoxy + thiol–ene” sequential dual click and “thiol–epoxy + Menschutkin chemistry + CuAAC” triple click strategies were presented, making functional group transformation readily accessible. Hydrophilic dendritic brushes, hydrophobic dendritic brushes and amphiphilic dendritic hetero-brushes were synthesized. Esterification of SHP containing hydroxy and azido groups with 1-pyrenebutyric acid yielded clickable fluorescent macromolecules, which showed a very strong excimer emission.