Electrochemical methods are well suited for chemical detection in hand-held devices because they are simple, fast, and sensitive. However, electrochemical detection methods generally suffer from limitations in selectivity. We report a novel approach that enables electrochemically initiated reactions to generate optical signals that can be used to enhance the discriminating power for the electrochemical analysis of antioxidant food phenols. This spectroelectrochemical approach employs transparent electrodes coated with a film of the aminopolysaccharide chitosan. The phenolic analytes diffuse through the chitosan film to the electrode where they are anodically oxidized into electrophilic intermediates that undergo postelectrode reactions with the chitosan film. The postelectrode reaction was analyzed by FTIR and XPS, and this reaction was observed to impart optical properties (color and UV-visible absorbance) to the otherwise colorless and transparent chitosan film. We demonstrate that the optical signal generated from the postelectrode film reaction is selective for oxidized phenols, compared to that for unoxidized phenols or the nonphenolic antioxidant ascorbic acid. Furthermore, we demonstrate that the optical signal (film absorbance) can be correlated to the electrical signal (charge transferred). Finally, we use simple mixtures to demonstrate that the coupling of information from independent optical and electrical measurement modes can assist in the qualitative analysis of antioxidant phenols. Potentially, the postelectrode film reaction may provide a selective and reagentless alternative to conventional colorimetric methods for detecting antioxidant phenols. In a broader perspective, this work suggests the potential for coupling independent detection modes (optical and electrical) to enhance the information content of sensor measurements.