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The processes of association of rhodamine‐6G molecules in aqueous solutions of polyacrylic acid are studied by spectroscopic methods. The efficiency of formation of the dimers of rhodamine 6G as a function of the concentration of the polyelectrolyte and its chain length is established. The angles between monomer molecules in the dimers of rhodamine 6G are determined for different concentrations of the polyacrylic acid and lengths of the polyion chain.