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The rapid development of 4D printing provides a potential strategy for the fabrication of deployable medical devices (DMD). The minimally invasive surgery to implant the DMD into the body is critical, 4D printing DMD allows the well‐defined device to be implanted with a high‐compacted shape and transformed into their designed shape to meet the requirement. Herein, a 4D printing tissue engineering material is developed with excellent biocompatibility and shape memory effect based on the photocrosslinked polycaprolactone (PCL). The fast thiol‐acrylate click reaction is applied for photocrosslinking of the acrylates capped star polymer (s‐PCL‐MA) with poly‐thiols, that enable the 3D printing for the DMD fabrication. The cell viability, erythrocyte hemolysis, and platelet adhesion results indicate the excellent biocompatibility of the 4D printing polymer, especially the biological subcutaneous implantation results confirm the promote tissue growth and good histocompatibility. A 4D printing stent with deformable shape and recovery at a temperature close to human body temperature demonstrated the potential application as DMD. In addition, the everolimus is loaded to the polymer (ps1‐PCL) through host‐guest coordination with β‐cyclodextrin as the core of the star polymer, which shows sustained drug release and improved body's inflammatory response. [ABSTRACT FROM AUTHOR]