The optical properties of the superdispersed system (SDS) KBr:Tl has been studied. The concentrations of Tl+ and Br- ions have been varied. The new data on the behavior of emission spectra in 2.2-4.1 eV range under the excitation in the range 4.4-6.0 eV have been obtained for SDS KBr:Tl at 77K. The random-walk method has been used for the decomposition and analysis of the strongly overlapped optical spectra. The origin of luminescent centers is discussed taking into account a partially covalent character of chemical bond, and the relaxation processes connected the with charge transfer. (C) 2014 Elsevier B.V. All rights reserved.