The removal of toxic halogenated pollutants in water is a topic of increasing urgency nowadays. Anthropogenic organic pollutants, especially per- and polyfluoroalkyl substance (PFAS), have seen increased concentrations in groundwater1 and drinking water.2 Due to their chemical persistence, bioaccumulation, and potential adverse health effects,3 these molecules are at the center of attention for environmental management. New selective separation technologies for targeting these contaminants from very diluted streams must be developed since traditional treatment methods lack molecular selectivity, may require extensive chemicals for regeneration, and often involve energy-intensive processes. Therefore, we developed a system that utilizes a redox copolymer capable of selectively adsorbing long-chain4 and short-chain PFAS, and mediating adsorption and release solely by electrochemical control. These redox electrosorbent is composed of poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl) (PTMA) and poly(4-methacryloyloxy2,2,6,6-tetramethylpiperidine) (PTMPMA), shortly denoted as PTMA-co-TMPMA. We were able to adsorb and desorb perfluorooctanoic acid (PFOA) up to 1,000 mg PFOA/g adsorbent in a batch system. We also found electrocatalytic breakdown for the shorter chain PFAS molecule hexafluoropropylene oxide dimer acid (GenX) during electrochemical reduction. Tandem electrosorption and electrochemical oxidation effect using boron-doped diamond (BDD) was also studied, by combining our redox-polymer electrodes with advanced oxidation counter electrodes. Finally, we introduced our redox copolymer electrode into a flow cell system capable of successfully adsorbing and desorbing fluorinated substances. We envision these integrated electrochemical reactive separation technologies to play an important role going forward for emerging contaminant remediation.