The generation of a uniform solid–electrolyte interphase film on the surface of the Li₄Ti₅O₁₂ anode at potentials above 1.0 V in an ethers electrolyte with lithium bis(trifluoromethanesulfonyl)imide as the lithium salt is reported. A significant enhancement in the cycling life can be obtained in the ethers electrolyte compared to in the conventional carbonates electrolyte. At a rate of 2 C, the discharge capacity can be retained at a stable 155.4 mA h g⁻¹ after 300 cycles with a high capacity retention of 97.5%, which is the best result reported for a Li₄Ti₅O₁₂ anode with a particle size above 300 nm.