The mechanical properties, morphology, and orientation of a poly(dimethylsiloxane) (PDMS) network have been studied during cyclic elongation and recovery by simultaneous Fourier-transform near-infrared polarization spectroscopy at temperatures ranging from room temperature to -40 degrees C. Completely different orientation/recovery mechanisms and changes in the state of order of PDMS were detected as a consequence of cyclic loading/unloading with decreasing temperature. The differences observed at -20 degrees C compared to room temperature are explained in terms of conformationally regular chain segments, whereas the cooling to -40 degrees C leads to the formation of lamellar crystals.