The photocatalytic oxidation of two selected organophosphorous insecticides (dichlorvos and dimethoate) has been investigated. The aim of the study was the identification of the intermediates that are formed during photocatalytic treatment. Intermediate products from the slurry system were identified by means of solid-phase extraction (SPE) coupled to gas chromatography–mass spectroscopy techniques (GC–MS). Nine possible by-products were identified for dimethoate and three for dichlorvos. A proposed degradation pathway for each insecticide is presented, involving mainly oxidation and dealkylation reactions. The results demonstrated that some of the transient intermediates formed (oxon derivatives, disulfide, chlorinated fragments), were more toxic compared to parent compounds whereas most of them are less toxic than the parent compounds.