Large and irregular bone defects remain a major clinical challenge, as critical-sized defects cannot heal through the body’s intrinsic regenerative capacity and typically require bone grafting. Irregularly shaped defects further increase surgical complexity and the risk of secondary damage. In this study, a temperature-responsive shape memory polymer poly(lactide-co-caprolactone) (PLCL) with a transition temperature close to physiological conditions was synthesized via ring-opening copolymerization of L-LA and ε-CL monomers at an optimized reaction temperature of 150 °C. PLCL scaffolds were successfully fabricated by selective laser sintering (SLS) 3D printing and exhibited shape fixation and recovery rates both exceeding 90% at 37 °C, enabling precise conformity to the edges of irregular bone defects. The scaffolds also demonstrated mechanical properties matching those of cancellous bone, with a tensile modulus of 138.23 ± 13.02 MPa and a tensile strength of 5.43 ± 0.71 MPa. These results suggest that SLS-printed PLCL scaffolds provide a promising strategy for repairing large, irregular bone defects.