The use of a thio‐bromo click strategy as an efficient postpolymerization tool is described. Norbornene derivatives bearing an α‐bromo ester could be polymerized using Grubbs 2 nd generation initiator to provide α‐bromo ester‐containing homo‐and block copolymers that could be efficiently functionalized through reactions with various thiols. A one‐pot strategy was also used, in which up to four different thiols were reacted simultaneously. This chemistry could also be used as an efficient cross‐linking strategy to form ROMP‐based gels as well as a tool for terminal functionalization of polypropylene‐based oligomers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.2016, 54, 179–185

A facile nucleophilic substitution between thiols and α‐bromo esters (thio‐bromo "click" reaction) was used for the postpolymerization modification of ROMP‐based materials. This metal‐free click approach allowed for a multiple functional groups to be installed in a one‐step, one‐pot process, providing reactions in high yields. This could also be applied toward the preparation of polymeric gels as well as terminally functionalized polyolefins.