• Supramolecular SSPCM based π-π stacking was prepared by facile block copolymerization of PEG, MDI and BP. • SSPCM shows super toughness and solid state even at 130 °C. • The light responsiveness and thermal conductivity of SSPCM have been improved by simple addition of CNT. The solid–solid phase change materials (SSPCMs) have become the preferred materials in thermal energy storage via absorbing latent heat from ambient environment. However, the trade-off between the mechanical properties, stability and recyclability is still the obstacle and barrier for development of SSPCMs. Herein, we proposed a facile and novel strategy to prepare SSPCMs for address above issues by introducing π-π stacking to form physical crosslinking points in linear polyethylene glycol (PEG). The strong intermolecular forces formed by π-π stacking not only prevented leakage of the PEG even at 130 °C but imparted high temperature stability and excellent toughness (172.44 MJ/m 3 ) to fabricated SSPCMs. It is worth mentioning that the prepared PCMs can be added with CNT in a simple process way to improve the photo-thermal conversion ability and thermal conductivity of SSPCMs. Besides, the as-prepared SSPCMs exhibited excellent flexibility, and were expected to be excellent thermal/photo energy storage materials for human thermal management and wearable devices.