The concentration dependence of the spectra of ionic and neutral dyes encapsulated in mesoporous silicate films is studied. A mesoporous dyed SiO2 film was prepared by the sol-gel technology with the use of amphiphilic three-block copolymer Pluronic P123 as a surfactant. It is found that if the dye concentration exceeds the mesoporous one, the new spectral bands appear that are distinct from those of initial monomolecular predecessors. To explain the phenomenon, it is assumed and proved that the origin of new spectra is due to the formation of ionic pairs, excimers, and excitons with participation of dye molecules localized at the characteristic places of the mesoporous silicate film.