The environmental fate of anionic per- and polyfluoroalkyl substances (PFASs) is of particular concern due to their toxicity and potential risks to human health and ecology. Various treatment approaches have been evaluated by researchers, with the most promising and readily applied ones being the adsorption technologies. However, the bulk of studies regarding the removal of PFAS anions from water have been limited to legacy compounds like perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Additionally, few studies were able to provide mechanistic comparisons between the conventional carbonaceous adsorbents and the emerging adsorbents for PFAS adsorption. Furthermore, a better understanding of the adsorptive behaviors in real aquatic matrices is urgently needed to inform the development of cost-effective PFAS remediation strategies. This study was designed to more fully explore the factors that influence the adsorption of anionic PFASs by coupling batch removal experiment results with multivariate data analysis. Based on the examination of 20 target PFASs and five different adsorbent materials in Milli-Q water and real groundwater samples, a classic multi-dimensional data visualization method was employed to help extract the principal associations. The distinct performance of adsorbents was attributed to their different surface chemistry and the distinct nature of their adsorption binding sites. pH, divalent, and monovalent cations are the primary contributors to adsorbent fouling in groundwater samples. The molecular structures and functional groups of PFASs also affected their adsorption behaviors. Knowledge of PFAS adsorption mechanisms gained from this study can be utilized to design more efficient adsorbents and to predict their performance under a range of environmental conditions.