Rate constants of decomposition of living polymeric adducts polystyrene (PS)-TEMPO, poly-4-vinylpyridine-TEMPO, PS-SG1, and polyacrylic acid-SG1 in different solvents were determined by the method of a competitive inhibition by means of electron spin resonance. It was found that with the increase in polarity of solvent, the values of constants become higher for all systems studied. This effect opens a new way of activating chains in nitroxide-mediated radical polymerization. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012