It has been suggested in an early study that sulfanes may serve as a source of sulfur contained in hydrogen sulfide sources. We have performed derivatization of sulfanes known to be present in the «Novonukutskaya» mineral water. The presence of polysulfanes in balneotherapeutic sulfide waters was confirmed by the HPLC-UV and chromato-mass spectrometric techniques. Derivatization of inorganic polysulfides was achieved by using the reaction with methyl iodide. It was shown that polysulfanes contained in the examined samples were metastable and disintegrated into So and H2S. Almost all molecular zero-valent sulfur was present in the form of S8. The application of HPLC allowed to determine the equilibrium concentration of molecular sulfur. The presence of the above compounds in therapeutic sulfide waters raises the question of the mechanism of their curative action. The authors hypothesize that it may be related to the high therapeutic potency of the substances obtained by steam distillation from the «Novonukutskaya» mineral water.