One kind of gel polymer electrolytes (GPE) with high performances based on polyacrylonitrile and green natural lignocellulose (LC) has been prepared. This as-prepared GPE exhibits excellent performance. When the proportion of LC reaches up to 60 wt%, the prepared composite membrane has a liquid electrolyte uptake of 673 wt% at room temperature, and the corresponding GPE-60 presents an ultrahigh lithium ion transference number of 0.84, high electrochemical stability and excellent specific capacity (143.90 mAh g(-1) at 0.2 C at 90th cycle of LiFePO4||GPE-60||Li). These advantages prove that the GPE-60 has great potential for the application of lithium ion batteries.