Formation of Cu(II) complexes of 1,2-dialkylmidazoles (where 1-alkyl=ethyl, propyl, butyl, pentyl, and hexyl, and 2-alkyl=propyl, butyl, and pentyl) has been studied using the liquid-liquid partition method, at 25C and at a fixed ionic strength of the aqueous phase (I=0.5; (HL)NO3, KNO3). The complexes were extracted with 2-ethyl-1-hexanol, and chloroform. The length of the 1-alkyl, and 2-alkyl groups, and the solvent nature have been shown to influence the extraction process. Extraction curves (log DM vs. pH) are displaced towards lower pH with increasing chain length of the 1-alkyl and 2-alkyl substituents. Stability constants of the complexes in aqueous solution as well as their partition constants between the aqueous and organic phase were determined. The stability of the Cu(II) complexes increased with increasing 1-alkyl chain length. The stability constants were comparable with n values for the Cu(II) complexes of 1-alkyl-2-ethylimidazoles, but smaller than those of the Cu(II) -1-alkylimidazole counterparts. The length of the 2-alkyl substituent has been found to affect both the pH1/2 values and the partition constants of the complexes. The partition constants P1 are small for all of the 1,2-dialkylimidazole complexes with Cu(II), whereas P2 and P3 are high and they increase with elongation of the 1-alkyl chain owing to a decrease in the co-ordination number of Cu(II), probably from 6 to 4 at the second and third complexation step. This change is likely to produce square coplanar species, readily extractable with organic solvent. This finding offers the possibility of extraction of the Cu(II) ions from a mixture cations.