Perfluorooctanoic acid (PFOA) and its analogs, such as perfluorocaproic acid (PFHxA), perfluorobutyric acid (PFBA), and perfluoro(2-methyl-3-oxahexanoic) acid (GenX), present environmental contamination concerns due to their toxicity. To addressing this, in this study, we have explored the utility of thermoplastic polyurethane/polyethyleneimine (TPU/PEI) nanofibers, synthesized via electrospinning, for the efficient removal of PFOA and its analogs from aqueous solutions. Combining the positively charged amino groups of PEI and hydrophobicity of TPU potentially enhances adsorption. Further, the TPU/PEI nanofibers exhibit a distinctive nano-phase separation morphology, creating abundant adsorption sites conducive to PFAS binding. Batch adsorption experiments indicated that TPU/PEI nanofibers possess notable adsorption capacities for PFOA and its analogs. The observed adsorption capacities were ranked as follows: PFOA (0.931 mmol/g) > PFHxA (0.872 mmol/g) > PFBA (0.827 mmol/g) > GenX (0.771 mmol/g), thus showing a correlation with their respective octanol–water partition coefficient (Kow) values. Both inorganic ions and organic matter exerted more pronounced adverse effects on the adsorption of PFBA and GenX than on those of PFOA and PFHxA. This observation can be linked to competitive adsorption with PFAS. Impressively, the TPU/PEI nanofibers maintained a high removal efficiency across multiple regeneration cycles, with more than 95 % adsorption capacity retained after five cycles. To the best of our knowledge, this study is the inaugural demonstration of utilizing a TPU and PEI blend for remediation of both long-chain and short-chain PFAS in highly polluted wastewater, positioning it as a promising, accessible material for such applications.