Photolysis may represent an important degradation process of pollutants at the surface of soil. In the present work, we report a detailed study on the degradation of two pesticides: mesotrione and metsulfuron methyl using a sunlight simulator. In a first step, we studied the photochemical behaviour at the surface of clays from the kinetic as well as from the analytical point of view. In both cases, the quantum yields were found to be higher when compared to those obtained in aqueous solutions. The effect of iron(III), water, and humic substances contents was studied. In the former cases, an increase of the degradation rate was observed while an inhibition was observed with the latter owing to a filter effect phenomenon. In a second step, we studied the photodegradation at the surface of natural soil and identified the generated byproducts. They appear to mainly arise from photohydrolysis process.