A high-performance gel polymer electrolyte (GPE) based on polyvinylidene fluoride (PVDF) and natural lignocellulose (LC) was successfully prepared via a simple coating method. The mechanical strength of the composite membrane is greatly enhanced and the dissociation of lithium salt is significantly promoted. Additionally, when the content of PVDF is 30 wt%, the prepared composite membrane presents high liquid electrolyte (LE) uptake (205 wt%) and excellent thermal stability. The corresponding GPE exhibits high ionic conductivity of 1.44 mS cm⁻¹ and good compatibility with the lithium anode. Moreover, the corresponding Li‖GPE‖LiFePO₄ battery maintains a relatively high capacity after being tested for 300 cycles at a rate of 1.0C, showing excellent cycle performance.