A solvent extraction study with 18-crown-6, 24-crown-8, and their dibenzo-derivatives has revealed that the following ligand–cation combinations give dicationic complexes in the solution phase: 18-crown-6 with Li+; 24-crown-8 with Li+, Na+, K+; dibenzo-24-crown-8 with Na+, K+, Ag+, Sr2+. The facile formation of dicationic complexes in the solvent extraction is attributed to the effective charge-shielding co-ordination by the bulky, lipophilic picrate anions in the contact ion-pair complex extracted.