A recently developed ultrarapid scanning Fourier transform infrared (URS-FTIR) spectrometer has been used to study the irreversible deformation of polymer films with a millisecond time resolution for the first time. The evolution of molecular orientation as a function of draw ratio and relaxation time was studied for films of amorphous poly(ethylene terephthalate) (PET) stretched above its glass transition temperature (T-g). Very good agreement was obtained between the results obtained by URS-FTIR and polarization modulation infrared linear dichroism (PM-IRLD) spectrometry. Reversible gauche-to-trans conversions were observed, indicating that the PET chains remain amorphous. The orientation and relaxation of polystyrene (PS) in films of pure PS and of blends of PS with poly(vinyl methyl ether) (PVME) were also studied above T-g. A method allowing the determination of the orientation function of PS using a single p-polarized spectrum is described. Results reveal a significant decrease in PS orientation during the first second following the end of deformation, emphasizing the importance of the experimental time resolution in the characterization of the relaxation behavior of polymers.