Abstract A glucose-based star-like block copolymer with a hydrophilic α- d -glucose core and amphiphilic block copolymer arms composed of n -butyl acrylate (BA) and oligo (ethylene glycol) acrylate (OEGA) has been synthesized for the first time via a simplified electrochemically mediated ATRP ( se ATRP) under both constant potential electrolysis and constant current electrolysis conditions, utilizing only 30 ppm of catalyst complex (significantly less than previously reported: 5000–50,000 ppm). The rate of the polymerizations was controlled by applying more positive potential values to prevent the possibility of intermolecular coupling of the polymer stars which are being formed and preparation of glucose-based star polymers with narrow molecular weight distributions. The lack of radical coupling reactions was confirmed by GPC analyses of the arm length of synthetized star (co)polymers. The results from 1 H NMR spectral studies support the formation of star-like block (co)polymers. It is expected that these new glucose-based star polymers may find application as biomaterials of an increased hydrophobicity and antifouling coatings.