This paper introduces the new synthetic methodology of polyolefin-based block and graft copolymers with polar segments [e.g., polystyrene and poly(meth)acrylates]. Various brominated polyolefins were prepared by bromination of polyolefins with N-bromosuccinimide. The resulting brominated polyolefins were able to initiate the controlled radical polymerization of polar monomers, such as methyl methacrylate, ethyl acrylate, t-butyl acrylate, styrene and 2-(dimethylamino)ethyl acrylate, using a CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalyst system, leading to a variety of polyolefin-based copolymers with a different content of the corresponding polar segment. Because of the accessible synthesis of polyolefin macroinitiators, this synthetic methodology is expected to result in the preparation of a wide range of polyolefin-based block and graft copolymers
