Mixed-chelate copper(II) complexes with a general formula [Cu(acac)(diamine)]X where acac = acetylacetonate ion, diamine = N,N-dimethyl,N′-benzyl-1,2-diaminoethane and X = BPh4−, PF6−, ClO4− and BF4− have been prepared. The complexes were characterized on the basis of elemental analysis, molar conductance, UV–vis and IR spectroscopies. The complexes are solvatochromic and their solvatochromism were investigated by visible spectroscopy. All complexes demonstrated the positive solvatochromism and among the complexes [Cu(acac)(diamine)]BPh4·H2O showed the highest Δνmax value. To explore the mechanism of interaction between solvent molecules and the complexes, different solvent parameters such as DN, AN, α and β using multiple linear regression (MLR) method were employed. The statistical results suggested that the DN parameter of the solvent plays a dominate contribution to the shift of the d–d absorption band of the complexes.