An organo gel with only 6 wt % tetra-armed poly(ethylene glycol), TetraPEG, was prepared and applied as a novel gel electrolyte for Li ion batteries (LIBs). The TetraPEG gel electrolyte containing 1.0 M LiPF6 in binary or ternary mixtures, i.e., EC + DEC and EC + DEC + TFEP (EC: ethylene carbonate, DEC: diethyl carbonate and TFEP: tris(2,2,2-trifluoroethyl)phosphate showed high ionic conductivity required for the use in LIB systems. The TetraPEG gel based on ternary EC + DEC + TFEP system acts as a nonflammable gel electrolyte at the TFEP content higher than 20 vol%. In cyclic voltammetry and charge/discharge cycling tests, the TetraPEG gel electrolytes showed good reversibility for a graphite negative electrode.