A series of polydimethylsiloxane (PDMS)/polycarbonate (PC) block copolymers with varying compositions were investigated by simultaneous mechanical and Fourier transform near-infrared (FTNIR) spectroscopic (rheo-optical) measurements to study segmental orientation during elongation-to-break and cyclic elongation-recovery procedures. Depending on the composition and the block lengths of the copolymers, different orientational and recovery phenomena were observed for the hard (PC) and soft (PDMS) segments.