Polyacrylonitrile (PAN)/organic montmorillonite (OMMT) membranes served as a host which is swelled using a liquid electrolyte of 1.0 M LiPF6 in carbonate solvent for gel polymer electrolyte have been fabricated by non solvent induced phase separation (NIPS) method. The OMMT fillers have affected the morphology, thermal stability, electrolyte uptake, ionic conductivity and electrochemical properties of PAN/OMMT membranes in different ways. The PAN/OMMT membrane exhibits high liquid uptake (375.5%), superior dimensional stability under 150 degrees C for 15 min and superior electrochemical stability up to 4.62 V. Moreover, the gel polymer electrolyte based on PAN/OMMT membrane not only possesses lower polarization and interfacial resistance, but also effectively suppresses the formation of Li dendrites as reflected in the surface morphology of lithium anode after cycling test. The application of natural montmorillonite has been demonstrated by a coin cell using Li metal as counter electrode at 1 C, resulting in the high capacity of 141 mAh g(-1) after 100 cycles and high capacity retention of 95.9%. The possibility of PAN/OMMT membrane applied for the sustainable safety lithium ion battery can be realized.