Conventional distillation methods cannot separate compounds with similar boiling points, molecular sizes, and volumes, such as cyclohexane and benzene or methylcyclohexane and toluene, effectively. The corresponding cyclic aliphatic and aromatic hydrocarbons cannot be separated effectively using the same type of sorption material. We report that crystalline thiacalixarene assemblies featuring preorganized channel-like adsorption sites are capable of both separations.