In the present work Principal Component Analysis applied to (1)H NMR spectra of balsamic and traditional balsamic vinegars is used to establish a simple and rapid aging determination protocol. Chemical composition of vinegar is dominated by carbohydrates even though several small components can be clearly observed in the proton NMR spectrum. Quantitative determination of some selected metabolites such as ethanol, acetic acid, malic acid, glucose, and HMF, considered as potential aging indicators, has been performed. (1)H NMR spectroscopy provides noninvasive characterization of such compounds, and our data demonstrate the validity of this approach, giving very promising results for assessing the quality of the final product.