A comprehensive summary of research work related to applications of NMR spectroscopy in combination with multivariate statistical analysis techniques for the analysis, quality control, and authentication of wine is presented. NMR spectroscopy is used to obtain the non-volatile metabolic profile and/or phenolic profile of wines, with the help of 2D NMR spectroscopy. Metabolomics is then used as an analytical tool to investigate the variability of the metabolic profile of wines due to a series of different factors involved during wine production, including terroir, pedoclimatic conditions, vintage, vineyard practices, wine-making, barrel maturation, and aging. The discriminating power of the NMR-obtained wine metabolome is utilized as a wholistic analytical approach in efforts to authenticate wine with respect to important economic attributes, such as cultivar, vintage, and geographical origin.