Photodegradation of bensulphuron methyl, (methyl α-(4,6-dimethoxypyrimidin-2-carbamoylsulphamoyl)- o -toluate ester) was carried out in aqueous solution under UV light. The rate of photolysis followed first-order kinetics, with a half-life of 31.7  min at λ  =  254  nm and 41.3  h at λ  ≥  290  nm, with significant correlation coefficients (0.9898 and 0.9625, respectively). The main photoproducts in distilled water were identified with a diode array detector and mass spectrometry. The results indicate that different reaction pathways are followed: cleavage of the sulphonylurea bridge, desulphonylation, which can proceed either by a carbon–sulphur cleavage or a nitrogen–sulphur cleavage and contraction of the sulphonylurea bridge. A mechanism which accounts for the formation of the photoproducts is proposed [ABSTRACT FROM AUTHOR]