In this work, the solvation thermodynamics of the D3d and Ci symmetry conformations of 18-crown-6 are investigated by way of extended reference interaction site model (XRISM) calculations. A broad range of solvent conditions are explored; viz., water, carbon tetrachloride, and acetonitrile at 25°C and 1 atm. We find that the relative free energies of solvation between the D3d and Ci conformers display a strong dependence on solvent type with the D3d structure becoming increasingly favored as solvent polarity increases. Our study of acetonitrile shows that electrostatic effects alone (with no hydrogen bonding) are sufficient to stabilize the D3d conformer in solution. In addition to energetics, the structuring of the solvent in the vicinity of the solute is examined. We also consider the solvation of dibenzo-18-crown-6. Our results show that the attachment of lateral groups to the crown perturbs the solvent structure in largely a local manner.