A promising solid polymer blend electrolyte is prepared by blending of poly(ethylene oxide) (PEO) with different content of amorphous poly(propylene carbonate) (PPC), in which the amorphous property of PPC is utilized to enhance the amorphous/free phase of solid polymer electrolyte, so as to achieve the purpose of modifying PEO-based solid polymer electrolyte. It indicates that the blending of PEO with PPC can effectively reduce the crystallization and increase the ion conductivity and electrochemical stability window of solid polymer electrolyte. When the content of PPC reaches 50%, the ionic conductivity reaches the maximum, which is 2.04 x 10(-5)S cm(-1)and 2.82 x 10(-4)S cm(-1)at 25 degrees C and 60 degrees C, respectively. The electrochemical stability window increases from 4.25 to 4.9 V and the interfacial stability of lithium metal anode is also greatly improved. The solid-state LiFePO4//Li battery with the PEO/50%PPC blend solid polymer electrolyte has good cycling stability, which the maximum discharge specific capacity is up to 125 mAh g(-1)at a charge/discharge current density of 0.5 C at 60 degrees C.