A kind of gel polymer electrolyte (GPE) based on natural composite polymers matrix of lignocellulose (LC) and potato starch with higher comprehensive performance is prepared. This study reveals that when the content of potato starch is 5wt.%, the composite membrane presents 6 times tensile strength of pure LC membrane and high electrolyte uptake of 194%. Meantime, the ionic conductivity of 1.27mScm−1, lithium ion transference number of 0.79, wide electrochemical window and good affinity with electrodes for the as-prepared GPEs can be obtained. In addition, the Li/GPE/LiFePO4 cells display excellent initial discharge capacity, rate and cycling performances. Therefore, the high performance, low cost and biodegradable GPE with the optimized material proportion developed in this work for application in lithium ion batteries (LIBs).