Anion-exchange (AE) sorbents are gaining in popularity for the remediation of anionic per- and polyfluoroalkyl substances (PFAS) in water. However, it is unclear how hydrophobic and electrostatic interactions contribute to anionic PFAS retention. The goal of this study was to understand the effects of PFAS chain length and head group on electrostatic interactions between PFAS and an aminopropyl AE phase. Liquid chromatography–mass spectrometry (LC–MS) was used with an aminopropyl AE guard column to find relative retention times. The average electrostatic potential (EPavg) of each PFAS was calculated, which correlated positively with the PFAS chromatographic retention time, demonstrating the value of EPavg as a proxy for predicting electrostatic interactions between PFAS and the aminopropyl AE phase. The order of greatest to lowest PFAS AE affinity for an aminopropyl column based on chromatographic retention times and electrostatic interactions was n:3 fluorotelomer carboxylic acids (n:3 FtAs) > n:2 fluorotelomer carboxylic acids (n:2 FtAs) > perfluoroalkyl carboxylates (PFCAs) > perfluoroalkyl sulfonamides (FASAs) ∼ n:2 fluorotelomer sulfonates (n:2 FtSs) > perfluoroalkyl sulfonates (PFSAs). This study introduces a methodology for qualitatively characterizing electrostatic interactions between PFAS and AE phases and highlights that electrostatic interactions alone cannot explain the affinity of PFAS for AE resins in water treatment/remediation scenarios.