Syndiotactic polystyrene(sPS) makes clathrates with some organic solvent molecules between TTGG helical chains, it is so-called δ-form. On particular, annealing or extracted within restricted conditions, δ-form can be changed to mesophase which has highly regulated molecular cavities. In this study, the time-resolved FT-IR spectra of the sPS films containing δ-form with toluene were measured, in order to clarify the relationship between release process of toluene and conformation changes of sPS. From the results of FT-IR, TTGG content were decreased for the annealed sample, but this was increased for the acetone extracted one because amorphous phase can be changed to TTGG conformation by acetone. It was concluded that the solvent extraction method was a better technique to make a mesophase containing sPS membrane, in comparison with the case of annealing.