Attenuated total reflectance spectroscopy was used to study the orientation and deformation of molecular chains in polymers. Reflection and transmission spectra of the polytetrafluorinethylene (PTFE) films were obtained. Parameters of the macromolecule's degree of order were determined for the whole volume and for the surface layer of uniaxially orientated PTFE, and on this basis, we determined the character of dependence l(SL)(L), where l(SL) is the effective thickness of the surface layer and L is the film stretching degree.