The electrolyte membrane plays a vital role in the practical conduction application of lithium-ion batteries. In this study, a series of PVDF-HFP/MOF-5 composite electrolyte materials were harvested by incorporating MOF-5 into PVDF-HFP, presenting excellent electrochemical characteristics and mechanical properties. Importantly, the performances of the PVDF-HFP/MOF-5 composites depended greatly on the content of MOF-5 introduced and the channels change. The PVDF-HFP/MOF-5-II with a MOF-5 content of 2 wt% revealed optimal ionic conductivity of 1.20 × 10-3 S cm-1 and lithium ion transference number of 0.9 at room temperature, which shows potential application prospects in the field of electrolyte materials.