Surface active per- and polyfluoroalkyl substances (PFAS) find niche applications because of their high chemical and thermal stability, their incompatibility with both water and hydrocarbons, and their unique ability to render surfaces non-stick. [DOI: 10.1016/j.cocis.2022.101571] However, several widely used PFAS surfactants have been found extremely resistant to degradation, accumulate in the environment, and have long half-lives in humans, consequently causing great concern. [DOI: 10.3390/surfaces3040037] [DOI: 10.1016/j.jhazmat.2021.128137] In the context of separating PFAS surfactants from aqueous media, we research how such surfactants bind to polymers that are free in solution or cross-linked in networks. We report here on ammonium perfluorooctanoate (PFOA) association (mixed micelle) structure and interactions with poly(ethylene oxide) homopolymers and block copolymers in water, [DOI: 10.1016/j.jcis.2021.10.176] and on PFOA binding to cyclodextrin-containing polymer networks. [DOI: 10.1021/acsmaterialslett.2c00168] We also discuss how surfactant-polymer binding can be disrupted for the regeneration of PFAS-adsorbent materials. [DOI: 10.1039/d1cp00049g] A detailed description emerges on how polymer segments distribute within PFAS micelles, which is used to evaluate the potential of functional polymers for the sequestration of PFAS pollutants.