We report on the synthesis of one-dimensional (1D) Li4Ti5O12 nanofibers through electrospinning and their outstanding electrochemical performances. Li4Ti5O12 with a spinel structure is a promising candidate anode material for lithium rechargeable batteries due to its well-known zero-strain merits. In order to improve the electronic properties of spinel Li4Ti5O12, which are intrinsically poor, we processed the material into a nanofiber type of architecture to shorten the Li+ and electron transport distance using a versatile electrospinning approach. The electrospun Li4Ti5O12 nanofiber showed significantly enhanced discharging/charging properties, even at high rates that exceeded 10 C, demonstrating that the nanofiber offers an attractive architecture for enhanced kinetics.