Poly(acrylic acid) (PAA) derived carbon-centered radicals were generated either radiolytically of photolytically and their decay followed by photometry or EPR. At low pH, i.e. in the case of fully protonated PAA, the first half-life of their decay is one millisecond. With increasing deprotonation the half-lives increase up to a value of more than 20 minutes for the fully ionized form, i.e. by more than 6 orders of magnitude. This prolonged lifetime is due to repulsive electrostatic forces acting between highly charged chains preventing the radicals from approaching one another to the distance required for recombination and/or disproportionation. The electrostatic forces similarly influence the rate of intramolecular H-abstraction reactions. Half-lives of the corresponding peroxyl PAA radicals, although also strongly influenced by the degree of dissociation of the polyelectrolyte, do not reach such high enhancement values (approximately 3 to 4 orders of magnitude). This is interpreted as being due to the longer encounter distance in the case of peroxyl radicals.