A novel synthetic strategy for the synthesis of graft copolymers is reported. Block copolymers containing segments with stable nitroxyl radicals side groups were first prepared by anionic polymerization, which were then used as a precursor for the subsequent nitroxide-mediated radical polymerization (NMRP) of styrene. This way, block-graft copolymers with polystyrene side chains grafted from one of the blocks were successfully synthesized in a controlled manner. In addition, block-graft copolymers with grafted polystyrene chains and a poly(tertbutyl methacrylate) block were subjected to hydrolysis to yield the corresponding amphiphilic polymers. The structures and the molecular weight characteristics of the polymers were characterized by spectral and chromatographic analyses. The surface morphology of thus obtained polymers was also investigated by microscopic techniques. (C) 2019 Wiley Periodicals, Inc.