Exposure to environmental toxins has been linked to various human health conditions, with pollutants often exacerbating disease severity. Among these, per- and polyfluoroalkyl substances (PFAS) have gained attention due to their widespread presence in consumer products and industrial processes, leading to human exposure. PFAS have been associated with adverse health outcomes, including effects on liver function and cognitive performance. This study utilizes National Health and Nutrition Examination Survey (NHANES) 2011–2014 data to examine PFAS exposure and cognitive performance using the Word List Learning Test, Delayed Word Recall, Animal Fluency Test, and Digit Symbol Substitution Test (DSST), highlighting sex differences. Additionally, NHANES 2017–2020 data are used to investigate the relationship between perfluoroalkyl acids (PFAAs) and liver biomarkers (Gamma-Glutamyl Transferase, Aspartate Aminotransferase, Alanine Aminotransferase, and Total Bilirubin), focusing on menopausal status. Multivariable regression assesses sex- and menopause-specific vulnerabilities, providing critical insights for targeted strategies to mitigate PFAS-related health risks.