The transition metal disulfide layered crystals belong to the class of transition metal dichalcogenides (TX2), characterized by quasi-two-dimensional crystallographic structure [1]. The peculiar properties of these materials result from their layered structure ( 4 3 6 6 / h P mmc − D ), consisting of a covalently bonded T-X-T sheets linked by weak Van der Waals forces. Within each sheet there is a trigonal prismatic coordination between the metal and chalcogenide atoms. Owing to the layered structure the electronic properties of the transition metal dichalcogenides can by essentially modified by intercalation of different chemical species between layers. The iodine, bromine or chlorine usually used as a transport agents for crystal growth by halogen vapor transport, also can be treated as intercalants. The halogen molecule placed in the adjacent tetrahedral sites of the gap gives rise to the neutral radiative center with properties, similar to that of the isoelectronic impurities in GaP or Si, which provide the strong bound excitons luminescence of the indirect band gap semiconductor. The PL spectra of a 2H-WS2:Br2 crystal, as in the case of the synthetic 2H-MoS2:Cl2, consist of two parts: a short-wave excitonic region, which includes several sharp intense lines, and a relatively weak broad band [2, 3]. There were identified three zero-phonon spectral lines contributing to the excitonic emission intensity: A, B and C. When the temperature is increasing the PL intensity is redistributed from the long wavelength peak A to peaks B and C. In the whole temperature range where the excitonic luminescence is observed, the broad-band emission intensity remains practically constant. It was shown, that the PL spectral sharp lines being due to the recombination of the excitons bond on the centers formed by the halogen molecules. For example, in the natural MoS2, so called mineral molybdenite, and in the samples grown without any transport agents the excitonic luminescence were not observed. Thus, the intercalation of the transition metals dichalcogenides by halogen molecules provides a new potential use of these layered materials: now, besides applications in such important areas as photovoltaic solar cells, solid lubricants, or intercalation batteries, the TX2 compounds are of great interest as efficient luminescent materials in the near IR spectral region.