In this paper, 22 samples consisting of Balsamic vinegar of Modena and two Traditional Balsamic vinegar of Modena samples have been analyzed by means of (1)H NMR spectroscopy. Some selected resonances have been used for quantification and for T1 (spin-lattice relaxation time) measurements. Statistical protocols applied to NMR data for quantification of selected resonances revealed the possibility to differentiate the samples according to their ageing process. Additionally, T1 measurements revealed a strong correlation with the ageing process and these new data were added for improving the statistical model, which was used to predict T1 relaxation time of selected compounds for Balsamic vinegar samples. Our results indicate that the use of NMR data and statistical methods is a valid approach that can be successfully used for ageing characterization of Balsamic vinegar of Modena samples.