A novel macromonomer based on tri-functional poly (alkylene oxide) main chain with acrylate chain ends was specially designed and synthesized for gel electrolyte purpose. Various kinds of gel electrolyte, based on the crosslinked macromonomer, were prepared. Interfacial resistance between lithium electrodes and the gel electrolytes was measured. The significant decrease in interfacial resistance was observed during 4-6 h after assembling the cell. The discharge capacity of secondary cells with the gel electrolyte depended on the kind of liquid electrolyte incorporated in the gel electrolyte.