Nuclear magnetic resonance (NMR) spectroscopy is a versatile tool for probing structure, dynamics, folding, and interactions at atomic resolution. While naturally occurring magnetically active isotopes, such as 1 H, 13 C, or 15 N, are most commonly used in biomolecular NMR, with 15 N and 13 C isotopic labeling routinely employed at the present time, 19 F is a very attractive and sensitive alternative nucleus, which offers rich information on biomolecules in solution and in the solid state. This presentation will summarize the unique benefits of solution, solid-state and in-cell 19 F NMR spectroscopy for the study of biomolecular systems. Particular focus will be placed on the most recent studies and on unique and important potential applications of fluorine NMR methodology.