Contaminated water detoxification remains difficult due to the presence of persistent halo-organic contaminants, such as perfluorooctanoic acid (PFOA) and chlorophenols, which are chemically stable and resist conventional purification methods. Functionalized membrane-based separation and decontamination have garnered immense attention in recent years. Commercially available microfiltration membrane (PVDF) and polymeric non-woven fiber filters (glass and composite) are functionalized with poly(methacrylic acid) (PMAA) that shows outstanding pH-responsive performance and tunable water permeability under ambient conditions perfect for environmental applications. Polymer loading based on weight gain measurements on PMAA–microglass composite fibers (137%) and microglass fibers (116%) confirmed their extent of functionalization, which was significantly greater than that of PVDF (25%) due to its widely effective pore diameter. Presence of chemically active hydrogel within PVDF matrix was validated by FTIR (hydroxyl/carbonyl) stretch peak, substantial decrease in contact angle (68.8° ± 0.5° to 30.8° ± 1.9°), and decrease in pure water flux from 509 to 148 LMH/bar. Nanoparticles are generated both in solution and within PVDF using simple redox reactions. This strategy is extended to PVDF-PMAA membranes, which are loaded with Fe/Pd nanoparticles for catalytic conversion of 4-chlorophenol and PFOA, forming Fe/Pd-PVDF-PMAA systems. A total of 0.25 mg/L Fe/Pd nanoparticles synthesized in solution displayed alloy-type structures and demonstrated a strong catalytic performance, achieving complete hydrogenation of 4-chlorophenol to phenol and 67% hydrogenation of PFOA to its reduced form at 22–23 °C with ultrapure hydrogen gas supply at pH 5.7. These results underscore the potential of hybrid polymer–nanoparticle systems as a novel remediation strategy, integrating tunable separation with catalytic degradation to overcome the limitations of conventional water treatment methods.