Abstract Phenols are well known as a class of pollutants that have a fouling effect on the electrode during electrochemical detection. The paper focuses on the investigation of the antifouling ability of Au/PPy and Au/PPy/PSS modified electrodes, during phenols electro-oxidation by electrochemical surface plasmon resonance technique (ESPR). The PPy and PPy/PSS films were electrochemically grown and followed by ESPR. Insertion of PSS − ions into the PPy film, observed by SPR and FTIR, has an important influence of the surface wettability, improving the hydrophilic character. The results have shown that the best antifouling effect was found for PPy/PSS surface during phenol electro-oxidation. The polyphenol or other reaction products accumulation rate is about ten times lower for PPy/PSS surface comparing with PPy film. Only isolated islands of polyphenol which electrochemically block only a lower part of the PPy/PSS surface were observed by SEM analysis. During CV scans in phenol solution, a linear increase of the SPR response evolution was found corresponding to the average accumulation rate of reaction products on the PPy/PSS surface. A good linear dependence of the SPR response with phenol concentration on the range 0.1–5 ppm was also obtained.