AbstractThe barocaloric effect (BCE) has emerged as an intense research topic in regard to efficient and clean solid-state refrigeration. Materials with solid-liquid phase transitions (SL-PTs) usually show huge melting entropies but cannot work in full solid-state refrigeration. Here, we report a colossal barocaloric effect realized by exploiting high entropy inherited from huge disorder of liquid phase in amorphous polyethylene glycol (PEG), which is solidified by introducing 5 wt.% polyethylene terephthalate (PET). Transmission electron microscopy (TEM) combined with X-ray diffraction (XRD) demonstrates the amorphous nature of the high-temperature phase after fixation by PET. Although PEG loses its –OH end mobility in amorphous solid, high entropy still retains owing to the retained high degrees of freedom of its molecular chains. The remaining entropy of amorphous PEG is up to 83% of that of liquid PEG in PEG10000/PET15000, and the barocaloric entropy change reaches ΔS_p ∼ 416 J·kg⁻¹·K⁻¹ under a low pressure of 0.1 GPa, which exceeds the performance of most other BCE materials. Infrared spectra combined with density function theory (DFT) calculations disclose conformational change from the liquid to amorphous state, which explains the origin of the large entropy retained and hence the colossal BCE of the solidified PEG. This research opens a new avenue for exploring full solid-state barocaloric materials by utilizing genetic high entropy from huge disordering of liquid phases in various materials with SL-PTs.