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Homo and copolymerization of isoprene (IP) with small amounts (1–10 wt %) of glycidyl methacrylate (GMA) are conducted using controlled-living radical polymerization (CRP) mediated by nitroxides (NMP) at 120 °C and 1170 kPa in solution with toluene (30 wt % solids). N-tert-butyl-N-(2-methyl-1-phenylpropyl)-O-(1-phenylethyl) hydroxylamine (TIPAL) is successfully used as a control agent (unimolecular process) although other controllers are also tested (TIPNO and OH-TEMPO in a bimolecular process using BPO as initiator). Chain extension experiments demonstrate the livingness of the synthesized materials. Several additives (acetic anhydride, camphorsulfonic acid and glucose) prove effective in accelerating the reactions. All the successful polymerizations result in first-order kinetics with respect to the monomer, yielding average molecular weights (Mn) of about 75% compared to the theoretical Mn (Mn, theo) with dispersities (Ð) ranging from 1.2 to 1.7 depending on the agent used for control. Controlled grafts of poly (isoprene-co-GMA) are also attached to polyisoprene via nitroxide chemistry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45108.