Segmented liquid crystalline polyurethanes (LCPUE) have been studied by infrared spectroscopy. The nematic liquid crystalline hard domains act as physical cross-links and can be oriented by the application of mechanical strain. The orientation function achievable in the hard segments results from the combination of mechanical strain and stress-softening, Furthermore, elastic deformation induces the rearrangement of some hard segments in the mesophase into a more ordered packing. High-temperature infrared spectra have been correlated with thermal transitions of the LCPUE, and a liquid-liquid microphase-separated morphology above the isotropization of the mesophase appears to exist.