The synthesis, characterization, and postpolymerization functionalization of star copolymers by RAFT polymerization, using ethylene glycol dimethacrylate as the difunctional monomer for core formation via crosslinking, is presented in this work. The "arm first" approach was used for the synthesis of PDMAEMA(n)POEGMA(n) double-hydrophilic mikto-arm stars and PDMAEMA(x)PLMA(y) amphiphilic miktoarm stars, while the "core first" approach was used for the synthesis of (PDMAEMA-b-POEGMA)(n) double-hydrophilic star block copolymers. Methyl iodide was used as the quaternizing agent for the transformation of the star copolymers into strong cationic star polyelectrolytes, through reaction on the dimethylamino groups of PDMAEMA blocks. The stars were characterized at the molecular level by SEC and proton nuclear magnetic resonance. Preliminary light scattering experiments, using THF and H2O as the solvents, were performed in order to get information regarding the solution behavior of the novel star copolymers synthesized. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019