In this paper, atactic polystyrene/carbon disulphide (aPS/CS2) gel-dried film was prepared at low temperature. In such film ordered structure was formed through stacks of some stereoregular segments by accepting TTGG type conformation, which strongly depended upon the interaction of CS2 and polymer segments. The dynamics of interaction was studied by measuring FTIR spectra. With increasing temperature, the regular TTGG conformation transferred to less regular gauche TG conformation and the molecular chains relaxed.