Soils and groundwater are often contaminated by complex organic mixtures also called Non Aqueous Phase Liquids (NAPLs). Several techniques such as drilling, monitoring of soil gas or injection of tracers are traditionally used to quantify NAPLs in aquifers but are complex to perform. The use of natural soil gas such as 222Rn could be an easy and cheap alternative. This method requires the knowledge of the radon NAPL-water partitioning coefficients (Kn-w.). Once spilled on soil, NAPL will undergo degradation (evaporation, effects of sun light among others) and this degradation could impact the Kn-w. This study aims at investigating the partitioning coefficients of complex NAPLs such as commercial diesel fuel and gasoline in relation to degradation such as evaporation and UV-degradation. For that purpose, batch experiments and GCMS investigations were carried out. The results show different Kn-w for the commercial diesel fuel (60.7 ± 6.1) and gasoline (37.4 ± 5.6). The results also show different Kn-w behaviors in relation with degradation. Degraded diesel fuel display opposite Kn-w values (74.8 ± 7.5 and 25.1 ± 2.5 for UV degraded and evaporated diesel fuel, respectively), compared to fresh one. Degraded gasoline shows no significant variations of the Kn-w compared to fresh one. The molecular investigation reveals the removal of the most volatile fraction for the evaporation treatment, whereas UV-degradation do not have pronounced effects on the chromatogram pattern. For the gasoline molecular investigation, no difference is observed between the treatments excepted a very slight removal of the lightest compounds under evaporation. These results show that NAPL degradation have effects on the Kn-w for diesel fuel and no significant effects for gasoline, at least with these degradation paths. This Kn-w variation will have in fine effects on 222Rn activity interpretation and NAPL subsurface quantification.