In this chapter, the basic principles of high-resolution NMR relevant to metabolomics are reviewed, with an emphasis on practical aspects of experimental design, execution, and interpretation of the spectral data. This includes one- and two-dimensional NMR with isotope-editing techniques for metabolite identification, quantification, and positional isotopomer analysis. The principles of isotopomer analysis by NMR for pathway determination and flux analysis are introduced. These principles are illustrated with particular examples of simplified mixtures of common metabolites. Advanced approaches for speeding data acquisition, as well as additional experiments including prospects for three-dimensional NMR for ab initio identification of unknown metabolites, especially if metabolically labeled, are introduced.