The structural development of a segmented poly(urethane-urea) (PUU) elastomer containing a low concentration of hard segment during deformation was studied by simultaneous mechanical and optical measurements (rheooptical techniques). Specifically, in-situ wide-angle X-ray diffraction and small-angle X-ray scattering using synchrotron radiation and time-resolved Fourier transform infrared spectroscopy were applied to investigate the segmental orientation of PUU chains during cyclic elongation and recovery. Formation of two different domain microstructures is characterized with changes in strain. These microstructures consist of lamellar hard domains and highly stressed nanofibrils consisting of alternating hard and crystalline soft domains. By comparing the X-ray scattering and vibrational spectroscopic data, a morphological model of hard-and soft-segment microphase separation, orientation, and strain-induced crystallization in the soft segments was obtained.