The photolysis of polymethacrylic acid was studied in aqueous solutions as a function of pH, polymer concentration, polymer chain length, and small additions of electrolytes in the absence of oxygen with light of wavelength 2537 Å. The random chain scission constants decrease with increasing pH values. Small variations in polymer chain length and concentration and electrolyte concentration have no effect on the photolysis. Changes in the ultraviolet spectra with irradiation time are more pronounced at low pH values than higher ones. It is shown that the decrease in susceptibility to photolysis with increasing degree of ionization of the acid is not proportional to the decrease or increase of the number of COOH or COO− groups respectively. It is rather due to the same causes—that is changes in ionic atmosphere— which make the polymer chains uncoil with increasing ionization.