Therefore, a new kind of LC-SMPCs, termed SMPU-OOBAm, were prepared with PEG-based SMPU containing about 40 wt % hard segment as the polymer matrix, and OOBA mesogen as the LC fillers. This study investigates the effect of OOBA on the structure, morphology, and properties of the SMPU-OOBAm. Notably different from previous systems, the present LC-SMPCs show a successful combination of the liquid crystalline properties, triple-shape memory effects, and self-healing properties. In particular, the self-healing mechanism may be notably different from the common self-healing materials. Thus, this study may be useful in order to fundamentally examine the multi-functional properties, multi-responsiveness, and efficient actuating method of SMPs and polymer composites.