In this review, four examples of the NMR metabolomic approach to foodstuff investigation are reported. Different types of foodstuff of different origin (namely truffle, kiwifruit, lettuce, and sea bass), with different metabolite composition, processing, and storage procedures have been chosen to demonstrate the versatility and potentiality of NMR in the foodstuff analysis. Fundamental aspects of NMR methodology such as sample preparation, metabolites extraction, quantitative elaboration of spectral data, and statistical analysis have been described. Metabolic profilings of aqueous and/or organic extracts as obtained by one- and two-dimensional NMR experiments have been reported together with the results obtained from their statistical elaboration. Discrimination between wild and farmed sea bass and between genetically modified and wild lettuces as well as changes in the kiwifruit metabolic profiles monitored over the season have been investigated. For each foodstuff, some complementary findings provided by other analytical methods are also described to underline the importance of different analytical approaches to explore specific aspects related to foodstuff.