Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 <= pH <= 9. The results are rationalized in terms of O-2 reduction by photogenerated alpha-hydroxy radicals of the polymeric ketone in competition with radical radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O+ and OH- affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the alpha-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O-2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O-2 for the reducing radicals resulting in a consumption of the peroxide.