Abstract Syndiotactic polystyrene (s-PS) was blended with poly(ethylene glycol) (PEG) in 1,2-dichloroethane (DCE) solvent. The mixture became a homogeneous solution at 155 °C depending on the composition ratio of PEG to DCE. When the solution was cooled at the rate of 5 °C/min to room temperature, a thermoreversible gelation was occurred. Wide angle X-ray diffraction (WAXD) measurements revealed that the polymer chain of s-PS in the obtained gel was crystallized with a helical conformation, while that in the non-gelated sample was done with an all-trans planar zigzag conformation. After drying gelated samples at 70 °C for 24 h, a novel polymer blend type of the physical gel consisting of s-PS and PEG was obtained. Dynamic mechanical analysis (DMA) revealed that the physical gel had a high modulus and a long elastic plateau in the temperature range of −80–270 °C.