The phosphorothioate structure is highly present in several pesticides. However, there is a lack of information about its degradation process in air and the secondary pollutants formed. Herein, the atmospheric reactions of chlorpyrifos, one of the most world-used insecticide, and its main degradation product – chlorpyrifos-oxon – are described. The photo-oxidation under the presence of NOx was studied in a large outdoor simulation chamber for both chlorpyrifos and chlorpyrifos-oxon, observing a rapid degradation (Half lifetime < 3.5 h for both compounds). Also, the photolysis reactions of both were studied. The formation of particulate matter (aerosol mass yield ranged 6–59%) and gaseous products were monitored. The chemical composition of minor products was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as 3,5,6-trichloropyridin-2-ol and ethyl 3,5,6-trichloropyridin-2-yl hydrogen phosphate. An atmospheric degradation mechanism has been amplified based on an oxidation started with OH-nucleophilic attack to PS bond.