Free-standing gel polymer electrolytes with poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix plasticized with tetraethylene glycol dimethyl ether (TEGDME) were prepared and investigated. The as-prepared gel polymer electrolytes exhibited large operating window and acceptable ionic conductivity. When applied in lithium oxygen batteries, the gel polymer electrolyte could support a high initial discharge capacity of 2988mAhg−1 when a carbon black electrode without catalyst was used as cathode. Furthermore, the battery with gel polymer electrolyte can last at least 50 cycles in the fixed capacity cycling, displaying an excellent stability. Detailed study reveals that the gelling process is essential for the cycling stability enhancement. With excellent electrochemical properties, the free-standing gel polymer electrolyte presented in this investigation has great application potentials in long-life lithium oxygen batteries.