In this study, a novel stepwise extraction method has been examined. The guest molecules housed between the helices of the clathrate 8 form of syndiotactic polystyrene can be removed completely with this method. A systematic study of the preparation of a solvent-free mesophase (emptied clathrate) membrane, its helical and residual solvent contents, and its structural transformations has been performed. In this first attempt, an enhancement in the TTGG helical content has been observed in the extracted membrane, and a conceptual mechanism is proposed.