Stricter guidelines are progressively established to control the presence of perfluorooctanoic acid (PFOA) inwater bodies due to its toxicity and persistence in the environment. This study focused on the development of anelectrochemical sensor based on a molecularly imprinted poly(o-phenylenediamine) film to detect PFOA inaqueous matrices. A comparative evaluation of sensor fabrication and analytical performance was performed ongold (AuE) and glassy carbon (GCE) electrodes. Experimental conditions influencing electropolymerizationbehavior, template removal, polymer morphology, and PFOA recognition were studied. Characterizations usingelectrochemical techniques and Raman spectroscopy were correlated with analytical performance. These wereassessed in spiked buffer solution, yielding concentration-dependent trends over a wide dynamic range, withdetection limits of 23.0 and 20.2 ppt for the AuE and the GCE, respectively, meeting the sensitivity requirementsof current EU regulations. Selectivity was evaluated by studying sensor response in the co-presence of potentialinterferents. The sensor was then tested on real samples collected from a wastewater treatment plant. A minormatrix effect was registered in the filtered effluent, supporting the applicability of the sensor for rapid on-sitePFOA screening near regulatory thresholds.