2D correlation spectroscopy has been used to investigate the behavior of a clathrate sample of syndiotactic polystyrene including 1,2-dichloroethane (DCE) in the crystalline phase. Isothermal desorption of DCE at 80 degrees C was selected as the perturbation process, with time as external variable, and it was shown that the response function of the system was an exponential decay. The resolution enhancement brought about by 2D analysis and the possibility to identify the temporal relationship among asynchronously correlated events allowed us to gather information on host-guest molecular interactions and on the development of the crystal structure, not readily available with more conventional approaches. It was shown that a characteristic peak of the guest molecules, i.e., the CH2 wagging mode of the trans conformer at 1235 cm(-1), is significantly influenced by host-guest interactions taking place within the cavity of the s-PS clathrate. It was confirmed that the desorption of the guest molecules initially present in the amorphous phase of the sample takes place at a faster rate than the desorption of those included into the cavities of the crystalline phase. This effect, in turn, allowed us to discriminate between the peaks of DCE absorbed in the two phases. In terms of dynamic behavior, it was found that DCE peaks respond faster to the applied perturbation than the polymer peaks, and as for the polymer spectrum, the crystalline phase responds faster than the amorphous phase. The latter effect has been tentatively attributed to the occurrence of a mesomorphic phase.