The morphology and electronic structure of a Li₄Ti₅O₁₂ anode are known to determine its electrical and electrochemical properties in lithium rechargeable batteries. Ag–Li₄Ti₅O₁₂ nanofibers have been rationally designed and synthesized by an electrospinning technique to meet the requirements of one-dimensional (1D) morphology and superior electrical conductivity. Herein, we have found that the 1D Ag–Li₄Ti₅O₁₂ nanofibers show enhanced specific capacity, rate capability, and cycling stability compared to bare Li₄Ti₅O₁₂ nanofibers, due to the Ag nanoparticles (< 5 nm), which are mainly distributed at interfaces between Li₄Ti₅O₁₂ primary particles. This structural morphology gives rise to 20% higher rate capability than bare Li₄Ti₅O₁₂ nanofibers by facilitating the charge transfer kinetics. Our findings provide an effective way to improve the electrochemical performance of Li₄Ti₅O₁₂ anodes for lithium rechargeable batteries.