In this study, a series of novel shape memory polyurethanes (SMPUs) containing tertiary amine groups are prepared by designing hexamethylene diisocyanate (HDI)-N-methyldiethanolamine (MDEA) as soft segments and HDI-BDO as hard segments. The structure and properties of the MDEA-based SMPUs are investigated using FT-IR, NMR, DSC, TGA, DMA, POM and AFM. The results demonstrate that the MDEA-based SMPU is composed of an amorphous soft phase and hard phase. The hard phase is amorphous below 20 wt% hard segment content (HSC), whereas the HDI-BDO segments form a semi-crystalline hard phase above 30 wt% HSC. This morphology exhibits good thermally induced SMEs with 100 % shape fixity and more than 80 % shape recovery. Moreover, the MDEA-based polyurethanes are expected to be further multifunctionalized for antibacterial activity, biocompatibility, multi-responsiveness and many other properties. This work provides a new strategy for designing multifunctional shape memory polymers with amine-containing polyurethanes.