The gel polymer electrolyte based on semi-IPN (interpenetrating polymer network) structure for the protection of lithium metal electrode was successfully developed by ultraviolet (UV) radiation-curing method. A curable mixed solution consists of linear polymer (Kynar 2801), crosslinking agent (1,6-hexanediol diacrylate), liquid electrolyte (ethylene carbonate (EC)/propylene carbonate (PC)/1 M LiClO4), oligo(ethylene glycol) borate (OEGB) anion receptor, and photoinitiator (methyl benzoylformate). The OEGB was synthesized by the dehydrocoupling reaction of hydroxyl group in di(ethylene glycol) methyl ether with hydrogen in BH3 and characterized by 1H NMR. The presence of OEGB anion receptor in the protection layer could lead to an enhancement in the ionic conductivity, electrochemical stability, and the interfacial properties. The deposited lithium exhibited particle-like shape resulting from the introduction of the protection layer onto the lithium electrode surface. The unit cell based on the lithium anode protected with gel polymer electrolyte containing OEGB showed higher discharge capacity than that of the unit cell without OEGB after 100 cycles at C/2 rate (1.25 mA cm−2).