Multimaterial thermally drawn fibers are becoming important building blocks in several foreseen applications in surgical probes, protective gears, or medical textiles. Here, the influence of the thermal drawing parameters on the degree of polymer chain orientation, the related thermal shrinkage behavior, and the mechanical properties of the final fibers is investigated via thermo-mechanical testing and small- and wide-angle X-ray scattering (SAXS and WAXS) analyses. This study on polyetherimide fibers reveals that the drawing stress, which depends on the drawing speed and temperature, controls the thermal shrinkage behavior and mechanical properties. Furthermore, SAXS and WAXS analyses show that the degree of chain orientation increases with drawing stresses below 8 MPa and then saturates, which correlates with the amount of observed shrinkage. The use of this process-dependent polymer chain alignment to tune the mechanical and shrinkage properties of the fibers is highlighted and controlled bending multimaterial fibers made of two polymethyl methacrylates having different molecular weights are developed. Finally, a heat treatment procedure is proposed to relax the chain alignment and increase the dimensional stability of devices such as temperature sensors. This deeper understanding can serve as a guide for the processing of complex fibers requiring specific mechanical properties or enhanced thermal stability.