This paper presents the use of Li4Ti5O12 (LTO) as anode with ionic liquid gel polymer electrolyte (IL-GPE) for application in lithium ion batteries. IL-GPE was obtained by in situ photopolymerization method of a mixture of ethoxylated bisphenol A diacrylate (bis(AEA4) and 0.4 M solution of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (MPPipTFSI). The surface morphology of the IL-GPE was studied using scanning electron microscopy (SEM). Stable, porous and flexible gel polymer electrolyte characterized high ionic conductivity (0.64 mS cm−1 at 25 °C) and a wide electrochemical stability window (ESW) (4.8 V). The performances of LTO/IL-GPE/Li cell were tested by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge/discharge. Good charge/discharge capacities and low capacity loss at medium C rates preliminary cycling was obtained.