In this work, a bio-shape memory polymer (SMP) with high performance is prepared by using cellulose acetate (CA) as raw material. The materials exhibit good mechanical properties with tensile strength and elongation at break over 46 MPa and 115%, respectively. With hydrogen bond interaction as physically cross-linked points, the materials also present excellent dual-shape memory properties with shape fixation and shape recovery ratio of about 99% and 96%, respectively. Moreover, the materials show good triple-shape memory effect. The recyclability of the materials is also investigated and the results show that the reclaimed samples still hold high mechanical and shape memory properties. With the intrinsic biocompatibility and biodegradation of CA, the materials could be an attractive candidate for applications in smart biomedical devices. Furthermore, the usage of CA as SMP could expand the view of preparing bio-SMP in future.