Triple-shape memory behaviours of SMPU-OOBAm composites were examined in a thermo-mechanical analysis using a TA Instruments DMA800 with tension clamps in controlled-force mode. In this experiment, the rectangular samples were first elongated at 100 °C, and then fixed at 80 °C, while the second elongation and fixation were carried out at 80 °C and 0 °C, respectively. Thereafter, the two step shape recovery is tested each for 40 min at 80 °C and 100 °C, respectively. The strain deformation, strain fixation, and strain recovery process were recorded for analysis. Figure 11 presents the strain-time-temperature curves of P1, P2, P3, and P4, respectively. The PEG-based SMPU was reported to show only dual-shape memory effects in previous studies. However, Figure 11 demonstrates that all composites show a two-step shape recovery with typical triple-shape memory effects. For example, in sample P1, after 62% strain is deformed at 100 °C, only 38% strain is fixed at 80 °C because of the higher fixation temperature, which is ascribed to the crystallization of the OOBA crystals. However, more than 98% strain fixation is obtained when the temperature decreases to 0 °C because of the further crystallization of the soft phase of the SMPU matrix. During the strain recovery process, P1 recovers 62.6% strain at 80 °C, and the remaining 13.8% strain is quickly recovered when the temperature increases to 100 °C. Finally, more than 90% of the total strain is recovered after the temperature is maintained at 100 °C for approximately 20 min. The strain recovery temperature in the second step corresponds exactly to the crystal-melting temperature of OOBA (76 °C) as mentioned in the DSC and POM results. However, when the OOBA-content increases, the strain recovery ratio in the second step tends to reduce from 90% (P1), 79% (P2), and 78% (P3) to 77% (P4). One possible reason for this is that OOBA has lubricated the SMPU polymer chains as a plasticizer. Although the crystallizability of the hard segment of SMPU is enhanced, the OOBA molecules in the composites may destroy the entire network structure of SMPU, which results in permanent deformation. The shape recovery thus decreases as the OOBA-content increases. However, all composites show good triple-SME. Both the strain fixation and strain recovery are programmable. Therefore, the SMPU-OOBAm can potentially be used in smart optical devices, electronic devices, and sensors.