From a comparison of transfer activity coefficients, [γ(LM+)]PC,2 between propylene carbonate and solvent S2 of alkali or silver ions complexed with dibenzo-substituted crown ethers (L=DB-18-cr-6, DB-21-cr-7, DB-24-cr-8, DB-30-cr-10) it can be concluded that in the complex LM+ both L and M+ are solvated, particularly in solvents of high donicity, e.g., N,N-dimethylformamide. From the abnormally low ionic mobility of DB-30-cr-10K+ in acetonitrile and the high value of the association constant of the ion pair DB-30-cr-10KBr it is concluded that the outer solvent shell is stripped upon formation of the ligand separated ion pair. A linear relation is found between [log γ(LM+)]PC,2 and [logγ(M+)]PC,2 only when L is 18-cr-6, B-18-cr-6, or DB-18-cr-6. Deviation from the linearity of complexes of the larger dibenzo crown ethers is attributed to the flexibility of L. It is shown that solution of 18-cr-6, DB-18-cr-6 and DB-30-cr-10 is enthalpy assisted to a greater extent in acetonitrile than in methanol, while the entropy of solution is more favorable in the latter.