The review presents extensive data (from the works of the author and literature) on the structure ofC- andN-chlorophosphorylated enamines and the related heterocycles obtained by multipulse multinuclear1H,13C, and31P NMR spectroscopy. The use of phosphorus pentachloride as a phosphorylating agent for functional enamines enables the synthesis of variousC- andN-phosphorylated products that are heterocyclized to form various promising nitrogen- and phosphorus-containing heterocyclic systems.31P NMR spectroscopy is the most convenient, reliable and unambiguous method for the study and identification of organophosphorus compounds with different coordination numbers of the phosphorus atom, as well as for the determination of theirZ- andE-isomeric forms. An alteration of the coordination number of the phosphorus atom in the phosphorylated compounds from 3 to 6 leads to a drastic screening of the31P nucleus from about +200 to −300 ppm. The unique structural features of nitrogen–phosphorus-containing heterocyclic compounds are discussed.