One-dimensional Ce3+-doped Li4Ti5O12 (Li4Ti5− x Ce x O12, x = 0, 0.01, 0.02, and 0.05) sub-microbelts with the width of approximately 500 nm and thickness of about 200 nm have been synthesized via the facile electrospinning method. The structure and morphology of the as-prepared samples are characterized by XRD, TEM, SEM, BET, HRTEM, XPS, and AFM. Importantly, one-dimensional Li4Ti5O12 sub-microbelts can be well preserved with the introduction of Ce3+ ions, while CeO2 impurity is obtained when x is greater than or equal to 0.02. The comparative experiments prove that Ce3+-doped Li4Ti5O12 electrodes... exhibit the brilliant electrochemical performance than undoped counterpart. Particularly, the reversible capacity of Li4Ti4.98Ce0.02O12 electrode reaches up to 139.9 mAh g−1 and still maintains at 132.6 mAh g−1 even after 100 cycles under the current rate of 4 C. The superior lithium storage properties of Li4Ti4.98Ce0.02O12 electrode could be attributed to their intrinsic structure advantage as well as enhanced overall conductivity.