Lithium batteries with high energy density can be achieved only with a metallic-lithium anode in conjunction with solid polymer electrolyte. Unfortunately, the undesirable interfacial properties and the subsequent formation of a solid electrolyte interface (SEI) layer and poor ionic conductivity at ambient temperature hamper this system from being commercialized. In order to conquer these issues, numerous attempts have been made. Herein we report the preparation and electrochemical properties of a nickel-1,3,5-benzene tricarboxylate metal organic framework (Ni₃–(BTC)₂–MOF) laden-composite polymer electrolyte with a lithium salt (LiTFSI). The added Ni₃–(BTC)₂–MOF plays a vital role in enhancing the ionic conductivity, and the mechanical and thermal properties. The scavenging properties of the highly porous MOF significantly improved the Li/electrolyte interfacial properties. A 2032-type coin cell composed of Li/CPE/LiFePO₄ was assembled and its cycling profile is discussed.