This paper describes an interesting structure dependent thermo-reversible dissolution of organic molecules in the presence of β-cyclodextrin (β-CD) in N, N-dimethyllformamide (DMF). β-CD could influence the solubility of dissolved organic molecules, resulting in the precipitation of organic molecule–β-CD complex from the original transparent solution as the temperature is increasing, while the precipitate will be dissolved again upon cooling. Different organic molecule–β-CD complex precipitates corresponded to different turbid temperatures (T t ). No precipitates were observed solely for either organic molecules or β-CD in DMF when the temperature increased, indicating the structure dependent recognition of β-CD to organic molecules. This molecular recognition behavior had been successfully applied in the separation of xylene isomers in preparative scale.