The ubiquitous presence and persistence of per‐ and polyfluoroalkyl substances (PFAS) in the environment have raised concerns in the scientific community. Current research efforts are prioritizing effective PFAS remediation through novel sorbents with orthogonal interaction mechanisms. Recognized sorption mechanisms between PFAS and sorbents include hydrophobic, electrostatic, and fluorine‐fluorine interaction. The interplay of these mechanisms contributes significantly to improved sorption capacity and selectivity in PFAS separations. In this study, a primary/secondary amine‐functionalized polystyrene‐divinylbenzene (Sepra‐WAX) polymer was modified to create a fluorinated WAX resin (Sepra‐WAX‐KelF‐PEI). The synthesis intermediate (Sepra‐WAX‐KelF) was also tested to assess the improvement of the final product (Sepra‐WAX‐KelF‐PEI). The adsorption capacity of Sepra‐WAX, Sepra‐WAX‐KelF, and Sepra‐WAX‐KelF‐PEI, and their interactions with PFAS were evaluated. The effect of pH, ionic strength, and organic solvents on PFAS sorption in aqueous solution was also investigated. The sorbents showed varied adsorption capacities for perfluorooctanoic acid, perfluoropentanoic acid, perfluoro‐n‐decanoic acid, and hexafluoropropylene oxide dimer acid, with the average extraction capacity of the four analytes being Sepra‐WAX‐KelF‐PEI (523 mg/g) > Sepra‐WAX (353 mg/g) > Sepra‐WAX‐KelF (220 mg/g). Sepra‐WAX‐KelF‐PEI provided the highest adsorption capacity for all analytes tested, proving that the combination of electrostatic and hydrophobic/fluorophilic interactions is crucial for the effective preconcentration of PFAS and its future applications for PFAS remediation from aqueous solutions.