The popularity of insect repellents presents the opportunity for continuous human and environmental exposure to such chemical mixtures. Consequently, the effects of their chemical components on human health and environmental safety is significantly reliant on their stability and hence, residence times under typical environmental conditions. Hence, for the first time, a thorough density functional theoretical (DFT) study on some possible hydrolytic and photolytic degradation pathways is presented and applied in the derivation of a comprehensive kinetic model, allowing evaluation of the residence time of picaridin; a very popular insect repellent. These results show that picaridin undergoes very slow hydrolysis via two pathways which present activation free energy barriers (ΔG‡) of ca. 225 and ca. 247 kJ mol−1 due to the asynchronous formation of four-membered cyclic activated complexes in both cases. Similarly, their photolytic transformations occur via two pathways, both of which are limited by the formation of the initial radical cation.