AbstractWithin the field of shape-changing materials, synthetic chemical modification has been widely used to introduce key structural units and subsequently expand the mechanical functionality of actuator devices. The introduction of architectural elements that facilitate in situ control over mechanical properties and complete geometric reconfiguration of a device is highly desirable to increase the morphological diversity of polymeric actuator materials. The subject of the present study is a multiblock copolymer with semicrystalline poly(l-lactide) and poly(ε-caprolactone) (PLLA–PCL) segments. By harnessing the stereocomplexation of copolymer chains with a poly(d-lactide) oligomer (PDLA), we provide anchoring points for physical network formation and demonstrate how a blending process can be used to efficiently vary the mechanical properties of a shape-memory actuator. We investigate the effect of molecular structure on the actuation performance of the material in cyclic thermomechanical tests, with a maximum reversible shape change εrev′ = 13.4 ± 1.5% measured at 3.1 wt % of polylactide stereocomplex content in the multiblock copolymer matrix. The thermophysical properties, crystalline structure, and phase morphology were analyzed by DSC, WAXS and AFM respectively, elucidating the structure-to-function relationship in physically cross-linked blended materials. The work demonstrates a one-step technique for manufacturing a polymeric actuator and tuning its performance in situ. This approach should greatly improve the efficiency of physically cross-linked actuator fabrication, allowing composition and physical behavior to be precisely and easily controlled.