This contribution describes the polymerization of 2,2,6,6-tetramethylpiperidin-4-yl methacrylate by atom transfer radical polymerization (ATRP). Different catalytic systems are compared. The CuCl/4,4'-dinonyl-2,2'-dipyridyl catalytic system allows a good control over the polymerization and provides polymers with a polydispersity index below 1.2. The successful polymerization of styrene from PTMPM-Cl macroinitiators by ATRP is then demonstrated. Successful quantitative oxidation of PTMPM-b-PS block copolymers leads to poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl-methacrylate)-b-poly(styrene) (PTMA-b-PS). The cyclic voltammogram of PTMA-b-PS indicates a reversible redox reaction at 3.6 V (vs. Li+/Li). Such block copolymers open new opportunities for the formation of functional organic cathode materials. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013