<p>Shape memory polymers (SMPs) represent a paradigm shift in material science, uniquely capable of undergoing reversible shape transformations triggered by external stimuli, positioning them as pivotal in developing next-generation biomedical devices, aerospace components, and adaptive structures. Extensive research has been done on SMPs with a major focus on high-temperature programming methods, which can limit energy efficiency and applicability with temperature-sensitive materials. Additionally, while various SMP blends have demonstrated great potential, limited work has been done on the suitability for 3D printing these materials, particularly under high-strain and ambient temperature programming conditions. In this study, a three-component optimized SMP composition was evaluated by 3D printing via the Material Extrusion (MEX) technique and investigating its ambient temperature-programming behavior at high strains. The SMP formulation studied was a tailored blend of thermoplastic polyurethane (TPU), polycaprolactone (PCL), and an octadecane diol-based copolymer (OBC) that exhibits robust shape memory behavior, high strain tolerance, and efficient force generation. Rigorous thermal, mechanical, and shape recovery analyses, along with optimized printing parameters and consistent shape recovery rates of up to 90%, were achieved under dynamic mechanical analysis (DMA), even under ambient programming conditions. This work demonstrates the SMP composition’s potential for adaptive, self-deployable systems with 4D printing characteristics ideal for bio-inspired structures and artificial muscle fibers.</p>