This study investigates the fabrication and characterization of heat-responsive PLA/PU/MXene shape memory polymer blend nanocomposites with varying PLA content (10, 20, 30, and 50%) and a fixed MXene content of 0.5 wt.%. The results indicate significant improvements in mechanical properties, with the 50% PLA/PU/MXene blend showing a 300% increase in ultimate tensile strength and a 90% decrease in % elongation compared to pure PU. Additionally, the 50% blend exhibited a 400% increase in flexural strength. Microstructural analysis revealed dispersed pores and sea–island morphology in pure PU and the 50% PLA/PU/MXene blend. Thermal analysis using DSC showed an increase in crystallinity from 33% (pure PU) to 45% for the 50% PLA/PU/MXene blend, indicating enhanced crystalline domains due to the semi-crystalline nature of PLA and MXene’s influence on molecular ordering. TGA demonstrated a significant improvement in thermal stability, with the onset temperature rising from 185 °C (pure PU) to 212 °C and the degradation temperature increasing from 370 °C to 425 °C for the 50% blend, attributed to the rigid structure of PLA and MXene’s stabilizing effect. Shape memory testing revealed that the 30% PLA/PU/MXene blend achieved the best shape fixity and recovery with optimal performance, whereas higher PLA content diminished shape memory behavior.