Abstract: | In this paper, a triple shape memory material was prepared by ultra‐simple melt blending from poly(ε‐caprolactone) (PCL), poly(propylene carbonate) (PPC) and ethylene‐α‐octene block copolymer (OBC). The obtained material possessed a co‐continuous phase morphology and presented an excellent triple shape memory effect (triple‐SME). Theoretical prediction demonstrated that a special continuous phase morphology could be constructed by adjusting the proportions of the blend. Moreover, the results indicated that a close relationship existed between the phase morphology and the triple‐SME of PCL/PPC/OBC. The sample with 35 vol% PPC content contributed to the formation of a continuous phase morphology and exhibited the optimal triple‐SME. Additionally, the sample PCL/PPC/OBC (32.5/35/32.5) showed outstanding structure and performance stability during cycle loading–unloading tests, which evidenced the prominent cycling shape memory property (nearly 100% shape fixing and recovery of temporary shape). Overall, this work could provide an efficient, convenient and recyclable method to obtain high‐performance shape memory materials. © 2020 Society of Chemical Industry |