The solubility in the CuBr₂-NR₄Br-H₂O (R = Me, Et, n-Bu) ternary systems at 25°C was determined by the isothermal saturation method. Comparative analysis of the phase equilibria diagrams was done. The results obtained were interpreted in terms of the competition of two processes, association of tetraalkylammonium salts and copper(II) complex formation in water-salt systems.