We employed 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMImTFSI)-based gel polymer electrolyte (ILPE) of low viscosity to prevent the instability of the di-TEMPO organic (DTO) electrode with enhancement of the cycle ability and rate-capability. The gel polymer electrolyte was prepared by electrospinning process. The DTO//ILPE//Li cell showed high initial capacity of 80mAh g-1 for 1 C and 68mAh g-1 for 10 C-rate, which corresponds to 100 and 85% of theoretical capacity, respectively. The cycle ability and rate-capability were much improved by using of EMImTFSI-based gel polymer electrolyte without self-discharge.