Publisher Summary The chapter discusses the fluorine-19 nuclear magnetic resonance (NMR) spectroscopy. The chapter explores the fluorohydrocarbons, including fluorinated aliphatic hydrocarbons, fluoro- olefins and acetylenes, fluorinated cyclohydrocarbons, and fluoroaromatics. The chapter elaborates on the study of fluorinated pyridines and the data for a number of di- and tri- fluoropyridine derivatives. The spectra is essentially used to determine the position of the fluorine atoms and, although the meta F-F coupling constants are determined on comparison with the meta F-F coupling constants in fluoroaromatics. The spectra of 2-fluoro-3-methylpyridine are fully analysed and, by using double and triple resonance techniques, the signs of the F-H and H-H couplings are determined. The 19F spectra of a series of tetrafluoropyridines and the substituent shifts found in these pyridines are compared with those of the corresponding substituted benzenes. The parameters are presented in this chapter for the fluorination of tetrahydrofuran, using potassium tetrafluorocobaltate afforded 2,2,5,5-tetrafluoro-2,5-dihydrofuran and 2,2,5-trifluoro-2,5- dihydrofuran. The F parameters of tetrafluorothiophen and the 4- and 5- methoxy derivatives have been reported, and these parameters are also presented in the chapter. A number of new 4-substituted perfluoro-oxazetidines are prepared and the 19F parameters of some of these compounds given. The chapter describes the organo-metallic compounds.