Syndiotactic polystyrene films uniaxially stretched at different draw ratios, and including different crystalline (δ and γ) phases as well as clathrate phases with 1,2-dichloropropane, 1,2-dichloroethane, and 1-chloropropane, have been studied by combined infrared linear dichroism and X-ray diffraction measurements. Information relative to the orientation and mobility of trans and gauche conformers of these chlorinated guests in their clathrate structures with syndiotactic polystyrene has been achieved by comparison between experimentally evaluated and calculated vibrational transition moment directions of conformationally sensitive infrared peaks of the guest molecules.