We observed that the poly(p-phenylenevinylene) units in Langmuir monolayers of partly converted dimethoxy-substituted poly(p-phenylenevinylene) precursor polymers oxidize at the air-water interface. This reaction even happened in the dark and therefore can not be attributed to a photooxygenation reaction with singlet oxygen. We assume that ground-state triplet oxygen is polarized at the air-water interface and forms a weakly bound complex with the double bond to give a reactive intermediate state, which lowers the activation energy of the oxidation reaction. The air-water interface thus works as a catalyst in this reaction.