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Conventional shape memory polymers suffer the drawbacks of low thermal stability, low strength, and low shape recovery speed. In this study, main-chain liquid crystalline polyurethane (LCPU) that contains polar groups was synthesized. Graphene oxide (GO)/LCPU composite was fabricated using the solution casting method. The tensile strength of GO/LCPU was 1.78 times that of neat LCPU. In addition, shape recovery speed was extensively improved. The average recovery rate of sample with 20 wt % GO loading was 9.2°/s, much faster than that of LCPU of 2.6°/s. The enhancement in mechanical property and shape memory behavior could be attributed to the structure of LCPU and GO, which enhanced the interfacial interactions between GO and LCPU.