AbstractRedox‐initiated free‐radical polymerization of methyl methacrylate (MMA) and acrylamide (AAm) with poly(ethy1ene glycol) (PEG) using Mn(III) as reduction agent was carried out to yield PMMA‐block‐PEG‐block‐PMMA and AAm‐block‐PEG‐block‐AAm triblock copolymers. The principal parameters (concentration of the reactants, temperature) affecting the synthesis were examined. Block copolymers were characterized by 'H‐NMR and