Abstract: With the advances of polymerization chemistry, especially controlled radical polymerizations, big progress on the synthesis of various topological polymers has been achieved. Different synthetic strategies have been deve-loped, among them, the heterofunctional initiator method is a facile and feasible approach, and has been extensively applied. This review describes the research progress on the application of this synthetic strategy in the preparation of various topological polymers, including block copolymers, miktoarm stars, H-shaped copolymers, π-shaped copolymers, graft polymers and cyclic polymers, but this review does not cover all published papers on this aspect. This synthetic strategy is based on the combination of different polymerizations, especially controlled polymerizations, and the combination of different controlled polymerizations with coupling reactions, such as “click” reactions, Diels-Alder reaction and active ester reaction etc.. The heterofunctional initiators discussed in this review include not only small organic molecules but also the polymers containing two or more initiation or chain transfer functional groups; the latter is also known as macro multifunctional initiators, which can initiate different polymerizations independently.

Key words: Asymmetric bifunctional initiator, Controlled radical polymerization, Coupling reaction, Heterofunctional initiator, Topological polymer