In this study the possibility of using potentiometric multisensor system (e-tongue) based on solid-state membrane electrodes for express evaluation of various quality parameters in vegetable oils was investigated. Optimization of oil sample preparation procedures for potentiometric analysis was performed. It was shown that developed multisensor system is capable to distinguish vegetable oil varieties prepared from different raw materials and pure oils from their mixture. Important edible oil quality indicators, such as peroxide value (PV), p-anisidine value (p-AV), and concentration of total tocopherols (TT) can be predicted from potentiometric multisensor system response using multivariate data processing. The parameters under study have the following ranges: PV (0.0–4.0); p-AV (0.4–3.8); TT (37.0–100.7). Application of multivariate regression tools yielded root mean square errors of prediction: 0.5 meq/kg for PV; 0.8 arbitrary units for p-AV; 10 mg/100 g for TT, thus showing a good promise for development of fast and simple method for express quality evaluation.