Gel polymer electrolytes composed of acrylonitrile–methylmethacrylate (AM) copolymer and 1M LiClO4–ethylene carbonate (EC)/propylene carbonate (PC) are prepared. The ionic conductivity reaches 1.9×10−3 Scm−1 in a gel polymer electrolyte with 20wt.% of AM copolymer and 80wt.% of LiClO4–EC/PC at room temperature. These systems showed no solvent exudation from the matrix polymer due to enhanced compatibility between AM copolymer and organic liquid electrolyte. A Li/gel polymer electrolyte/LiMn2O4 cell has a reversible capacity of 132mAhg−1 in the voltage range of 3.0–4.3V at the C/5 rate and shows good cycling performance with a coulombic efficiency >99%.