For the development of thermal conducting shape memory polymer (SMP), a tetrathiafulvalene (TTF)-based reactive molecule (RM) is newly programmed and synthesized. The thermal, optical, and structural behaviours of TTF-RM are analysed using various experiments. The thiol groups of TTF-RM can be polymerized without any catalyst or initiator, so TTF SMP is obtained by simple thermal polymerization. TTF SMP exhibits excellent shape memory properties as well as an excellent thermal conductivity of 1.12 W/mK. The correlation between thermal conductivity and shape memory speed is confirmed through TTF SMP and IR camera prepared with different thicknesses. Finally, the applicability of TTF SMP is demonstrated through the fabrication of smart curtain and smart sensor. This work was supported by Basic Research Laboratory Program (2020R1A4A1018259), Mid-Career Researcher Program (2021R1A2C2009423), and BK21 FOUR program.