High-performance ion chromatography exclusion, inductively coupled plasma emission spectroscopy, and nuclear magnetic resonance (NMR) measurements were carried out in combination with chemometrics on 33 wine samples coming from three Slovenian wine-growing regions and from Apulia (southern Italy). The chemometric classification of wines according to their geographical origin was obtained with a nearly 100% degree of achievement. The discriminating potential of the H-1 NMR and of the other analytical determinations has been estimated separately. The best prediction of wines has been obtained with NMR data.