This paper describes a new type of LC-SMPU composites, which were prepared with PEG-based SMPU and OOBA mesogens. The effect of OOBA on the structure, morphology, and properties of the material was carefully investigated. The results demonstrate that the LC-SMPU composites have liquid crystalline properties, triple-shape memory properties, and self-healing properties. The incorporated OOBA promotes the crystallizability of both the soft and hard segments of SMPU. However, the isothermal crystallization kinetics revealed that the crystallization rate of the hard segment decreases when the OOBA-content increases. Additionally, the SEM confirmed that the SMPU-OOBAm composites form a two-phase separated structure, which was comprised of an SMPU phase and an OOBA phase. DMA further reveals that the composites show two-step modulus changes upon heating. Therefore, the SMPU-OOBAm composites exhibit triple-shape memory behaviour, but the shape recovery ratio decreases with the increase in OOBA-content. Because of the crystalline behaviours and LC properties of OOBA that are maintained in all SMPU-OOBAm composites, the SMPU-OOBAm composites have good self-healing properties, due to the heating-induced “bleeding” of OOBA in the liquid crystalline state and its subsequent crystallization upon cooling. Therefore, the SMPU-OOBAm composites have promising applications in smart optical devices, smart electronic devices, and smart sensors.