Topological polymers with T-shaped and H-shaped molecular architecture were built on the combination of atom transfer radical polymerization (ATRP) and UV-induced strain promoted azide-alkyne cycloaddition (SPAAC) reaction. In the presence of a cyclopropenone-masked dibenzocyclooctyne functionalized dibromo ATRP initiator, reactive polystyrene (PS) was synthesized to have a cyclopropenone-masked dibenzocyclooctyne group in the middle of polymer chain. After releasing dibenzocyclooctyne from deprotecting cyclopropenone-masked dibenzocyclooctyne under UV irradiation, T-shaped and H-shaped topological polymers were constructed by reacting PS with mono-end and di-end azide functionalized poly(ethylene oxide) (PEO), respectively, based on the SPAAC reaction. (C) 2016 Elsevier Ltd. All rights reserved.