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Dual-functional polymeric system combining shape memory with self-healing properties has attracted increasingly interests of researchers, as both of these properties are intelligent and promising characteristics. Moreover, shape memory polymer that functions at human body temperature (37 °C) are desirable because of their potential applications in biomedical field. Herein, we designed a polymer network with a permanent covalent crosslinking and abundant weak hydrogen bonds. The former introduces elasticity responsible and maintain the permanent shape, and the latter contributes to the temporary shape via network rearrangement. The obtained PDMS-COO-E polymer films exhibit excellent mechanical properties and the capability to efficiently self-heal for 6 h at room temperature. Furthermore, the samples turn from a viscous state into an elastic state at 37 °C. Therefore, this polymer has shape memory effects triggered by body temperature. This unique material will have a wide range of applications in many fields, containing wearable electronics, biomedical devices, and 4D printing.