A novel gel polymer electrolyte (GPE) based on polyethylene glycol (PEG) composite lignocellulose (LC) with compact structure for application in lithium ion batteries (LIBs) is prepared. The GPE membrane dramatically enhances mechanical properties, and displays as high as 3–4 times than that of pure LC when adopting 30% PEG-1000. Meanwhile, the increased liquid electrolyte uptake is obtained (267%), and caused high ionic conductivity (3.22mScm−1) at room temperature. Moreover, the lithium ion transference number is as high as 0.81, much higher than most of reported separators, and shows good thermal and electrochemical stability. The rate and cycling performances further confirm that the GPE a very promising candidate for LIBs.