The complexation reaction between UO22+ cation with macrocyclic ligand, 18-crown-6 (18C6), was studied in acetonitrile–methanol (AN–MeOH), nitromethane–methanol (NM–MeOH) and propylencarbonate–ethanol (PC–EtOH) binary mixed systems at 25 °C. In addition, the complexation process between UO22+ cation with diaza-18-crown-6 (DA18C6) was studied in acetonitrile–methanol (AN–MeOH), acetonitrile–ethanol (AN–EtOH), acetonitrile–ethylacetate (AN–EtOAc), methanol–water (MeOH–H2O), ethanol–water (EtOH–H2O), acetonitrile–water (AN–H2O), dimethylformamide–methanol (DMF–MeOH), dimethylformamide–ethanol (DMF–EtOH), and dimethylformamide–ethylacetate (DMF–EtOAc) binary solutions at 25 °C using the conductometric method. The conductance data show that the stoichiometry of the complexes formed between (18C6) and (DA18C6) with UO22+ cation in most cases is 1:1 [M:L], but in some solvent 1:2 [M:L2] complex is formed in solutions. The values of stability constants (log Kf) of (18C6 • UO22+) and (DA18C6 • UO22+) complexes which were obtained from conductometric data, show that the nature and also the composition of the solvent systems are important factors that are effective on the stability and even the stoichiometry of the complexes formed in solutions. In all cases, a non-linear relationship is observed for the changes of stability constants (log Kf) of the (18C6 • UO22+) and (DA18C6 • UO22+) complexes versus the composition of the binary mixed solvents. The stability order of (18C6 • UO22+) complex in pure studied solvents was found to be: EtOH > AN ≈ NM > PC ≈ MeOH, but in the case of (DA18C6 • UO22+) complex it was: H2O > MeOH > EtOH.