A novel multiple‐pair‐electrode detection system for high‐performance liquid chromatography was developed using track‐etched membrane electrodes arranged in series along the eluent flow. The system generates distinct anodic and cathodic response combinations from each electrode pair, individually polarized at specific potentials, effectively reflecting the electrochemical reaction reversibility of each component. These detection behaviors offer robust support for peak identification in complex chromatograms. The effectiveness of the proposed system was demonstrated through the identification and quantification of several phenolic compounds in commercially available coffee and green tea beverages.