A new thermoresponsive self-healing polymer thermoset ((1.5M/F)DA-PDMS-PU) based on the Diels–Alder (DA) reaction between furan and maleimide groups was developed. The material exhibited glass temperature induced shape memory effect that brings crack faces into intimate contact, enabling the reformation of DA bridges located in the crack surfaces. In addition, the incorporation PDMS segments and excess maleimide functional groups besides DA bridges in the network promotes the mobility of dynamic groups and the healing reaction, therefore increasing the ability of the material to heal damages at a mild temperature. Scratch healing was possible via a one-step heating process at a moderate temperature of 60 °C for 4 h, reaching a tensile strength recovery of above 85%.