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The role of mold temperature on the morphology and properties of rotational shearing polyethylene (PE) pipes was studied via a self-developed rotational shear system (RSS). The result indicated that when the mold temperature was 150 °C, the hoop tensile strength and Vicat softening temperature were enhanced rapidly, which were 383.6% and 137.9% higher than those of the conventional PE pipes, respectively. Morphology and crystal structure studies by SEM and DSC revealed that once the rotational shear was applied, the shish-kebab structure began to appear. With the increase of the mold temperature, due to the relaxation of most of the oriented molecular chains, the preservation of shish-kebab structure became difficult. When the mold temperature was 190 °C, only the inner layer of the pipes, where the cooling rate was the largest, could preserve the shish-kebab structure. According to WAXD, there was less shish structure, and the growth of kebab was distorted in the inner layer of the pipes at 210 °C. The result of SAXS suggested that the length of shish changed most within the temperature range from 170 °C to 190 °C. The results of DSC and WAXD showed less change in crystallinity and degree of orientation between the two temperatures. It can be concluded that the reduction of shish length leads to a decrease in mechanical properties and heat-resistance.