Precise theoretical predictions of 19F NMR parameters are helpful for the spectroscopic identification of crystalline metal fluorides, especially for metal fluorides that possess multiple crystallographic fluorine sites. Taking advantage of recent advancements in theoretical methods, 19F NMR chemical shifts of various crystalline metal fluorides have been theoretically calculated on the basis of the periodic structure models. The theoretical results reported herein are not only superior to the those predicted by conventional DFT calculation methods but also render possible refinement of crystallographic data and explicit chemical shift assignments, as exemplified by various metal fluorides containing multiple crystallographic fluorine sites, such as β-BaAlF5 and Ba3Al2F12.