In this study, four extraction methods of perfluoroalkyl substances (PFASs) in soils and sediments were validated and compared in order to select the one that provides the best recoveries and the highest sensitivity. The determination of PFASs was carried out by liquid chromatography-tandem mass spectrometry. The extraction methods compared were based on (i) an aqueous solution of acetic acid and methanol (recoveries 44-125%, relative standard deviation (RSD) <25%), (ii) methanol (34-109%, <25%), (iii) sodium hydroxide digestion (24-178%, <49%), and (iv) ion pair (35-179%, <31%). The best results were obtained with methanol extraction, which recovered a greater number of PFASs and provided values between 45-103% in sediment and 34-109% in soil with RSDs <25% and limits of quantification (LOQs) between 0.02-0.31 and 0.01-6.00 ng g(-1), respectively. The selected method was successfully applied to Segura River sediments and soil samples taken near the Turia River. This study demonstrates the presence of PFASs in the studied rivers of the Valencian Community (0.07-14.91 ng g(-1) in Segura River sediments; 0.02-64.04 ng g(-1) in Turia River soils). Graphical Abstract Selected matrices and extraction methods for determination of perfluoroalkyl substances.