AbstractThe hierarchical design approach provides various opportunities to adjust the structural performance of polymer materials. Electrospinning processing techniques give access to molecular orientation as a design parameter, which we consider here in view of the shape-memory actuation performance. The aim of this work is to investigate how the reversible strain ε′rev can be affected by a morphology change from a bulk material to an electrospun mesh. ε′rev could be increased from 5.5 ± 0.5% to 15 ± 1.8% for a blend from a multiblock copolymer with poly(ε-caprolactone) (PCL) and poly(L-lactide) (PLLA) segments with oligo(D-lactide) (ODLA). This study demonstrates an effective design approach for enhancing soft actuator performance, which can be broadly applied in soft robotics and medicine.