The formation processes for heterogeneous associates of cationic dyes in polyvinyl alcohol films are investigated. The influence of colorless anions on the heterogeneous association efficiency is established. The structures of heterogeneous dimers of various dyes in polymer matrixes are defined.Introduction. Polymeric laser elements that are both solutions of dyes [1] and polymeric matrices with incorporated molecules [2, 3] have recently become of great interest. The generating properties of such media are determined mainly by their spectral and luminescent characteristics. Complexes in the ground state (associates) that are associated states causing a change of the laser active medium spectral characteristics and also fluorescence quenching can be formed at high dye concentrations. The efficiency of association processes in polymeric systems with incorporated dye molecules depends on their structural organization and charges [4]. Association processes between various types of molecules (formation of heterogeneous associates) are interesting with respect to the use of multi-component luminescing systems for increasing the lasing energy and expanding the frequency range of its tuning. The interaction of only colored ions (cations) is usually examined in studies of formation processes of heterogeneous associates of dyes [5,6]. Therefore, an investigation of the influence of colorless anions on such processes is critical. Herein we report results from a study of association processes of dye molecules in polymeric matrices.Experimental. The following cationic dyes were studied: Rhodamine 6G (R6G) with various anions (Cl