A novel gel polymer electrolyte (GPE) is prepared based on polyvinyl alcohol (PVA) composite lignocellulose (LC). In this work, mechanical strength of PVA composite LC membranes is significantly enhanced, which endows corresponding GPEs with application potential in lithium ion batteries (LIBs). Meanwhile, when the content of PVA is 5 wt.%, GPE presents high enough liquid electrolyte uptake (425 wt.%) and enough thermal stability. At room temperature, the ion conductivity is 3.92 x 10(-3) S cm(-1) and lithium ion transference number is up to 0.63. In addition, GPE exhibits electrochemical stability window at 5.2 V (vs. Li/Li+), good compatibility with electrode, excellent initial discharge specific capacity, C-rate and cycling performances.