A simple HPLC-EC method based on hydrophilic interaction liquid chromatography with amperometric detection through gold screen-printed electrodes has been developed and applied for the first time to the determination of aminothiols in white wines. Moreover, the coupling of the method with partial least squares discriminant analysis (PLS-DA) using the analysed aminothiols as biomarkers provides wine discrimination in terms of harvest year. White wine samples were directly injected and chromatographic areas, together with pH and redox potential values, allowed a successful discrimination of wines from different harvest years with a global classification rate of 97.8%. The developed HPLC-EC method also generated characteristic fingerprints that were combined with PLS-DA to classify wines according to three wine varieties, with a global classification rate of 95.3%.