Lithium polymer cells composed of a lithium negative electrode and a LiCoO2 positive electrode were assembled with a gel polymer electrolyte obtained by in situ polymerization of an electrolyte solution containing an ionic liquid monomer with vinyl groups. The polymerization of the electrolyte solution containing the non-flammable ionic liquid monomer resulted in a significant reduction of the flammability of the gel polymer electrolytes. The lithium polymer cell assembled with the stable gel polymer electrolyte delivered a discharge capacity of 134.3mAhg−1 at ambient temperature and exhibited good capacity retention.