Per- and polyfluoroalkyl substances (PFAS) is a class of persistent organic pollutants that presents health and environmental risks. PFAS are ubiquitously present in the environment, but current remediation technologies are ineffective in degrading them into innocuous chemicals, especially high energy degradation processes often generate toxic short chain intermediates. Therefore, the best remediation strategy is to first detect the source of pollution, followed by capturing and mineralising or recycling of the compounds. The main objective of this article is to summarise the unique physicochemical properties and to critically review the intermolecular and intramolecular physicochemical interactions of PFAS, and how these interactions can become obstacles; and at the same time, how they can be applied to the PFAS sensing, capturing, and recycling process. The physicochemical interactions of PFAS chemicals are being reviewed in this paper includes, (1) fluorophilic interactions, (2) hydrophobic interactions, (3) electrostatic interactions and cation bridging, (4) ionic exchange and (5) hydrogen bond. Moreover, all the different influential factors to these interactions have also been reported. Finally, properties of these interactions are compared against one another, and the recommendations for future designs of affinity materials for PFAS have been given.