Viscoelastic phase separation (VPS) can happen in polymer modified bitumen due to the large dynamic asymmetry between polymer and bitumen. The network formation induced by VPS can enhance the rheological property of bituminous materials. In this SBS/PE modified bitumen, multiple phase separation involving VPS can occur due to the immiscibility between either two components of them. Moreover, the crystalline-to-amorphous phase transition of PE-rich phase also influences the rheological property due to its large amount of melting enthalpy. Two different composition ratios of SBS/PE are chosen to explore the correlation between phase transition and rheological property. The conclusion obtained by this study may enlighten the design of energy storage bituminous materials modified by polymer blend which possess crystalline-to-amorphous phase transition and viscoelastic phase separation.