AbstractIn this work a potentiometric electronic tongue based on an array of three Ion Selective Electrodes (ISEs) as sensor elements and multiway partial least squares (N‐PLS2) regression method as processing tool has been developed for simultaneous quantification of Cd2+, Cu2+ and Pb2+ in aqueous solution mixtures. The sensor array was formed by two chalcogenide glass sensors selective to Cd2+ and Cu2+ plus one PVC membrane sensor selective to Pb2+. Preparation, measurement and injection of samples in a step profile were performed by an automated SIA system. Concentration range covered was 1.05 µM to 29.8 µM for Cd2+, 0.05 µM to 1.5 µM for Cu2+ and 0.55 µM to 14.7 µM for Pb2+. Potentiometric recordings were arranged into a three‐way array and treated by N‐PLS2 regression method to obtain the calibration model. Prediction ability yielded RMSE values as low as 4.20±0.37 µM, 0.094±0.007 µM and 0.915±0.006 µM, and correlation coefficients from linear regression analysis of 0.82±0.038, 0.97±0.005 and 0.97±0.004 for Cd2+, Cu2+ and Pb2+, respectively.