Syndiotactic polystyrene(sPS) makes clathrates with some organic solvent molecules between TTGG helical chains, it is so-called δ-form complex. On particular, annealing or extraction 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 complex with toluene were measured, in order to clarify the relationship between release process of toluene and conformational changes of sPS. From the results of FT-IR, TTGG content decreased for the annealed sample, but swelling with 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.