Tiny Li4Ti5O12 nanoparticles embedded in carbon nanofibers (Li4Ti5O12@C hierarchical nanofibers) were synthesized using a scalable synthesis technique involving electrospinning and annealing in an Ar atmosphere for the purpose of using them as anode materials for high-capacity and high-rate-capability Li-ion and Na-ion batteries. The Li4Ti5O12@C hierarchical nanofibers exhibited high stable discharge capacities of about 145.5 mA h g(-1) after 1000 cycles at 10C for the Li-ion battery anode. For Na-ion storage performance, a reversible capacity of approximately 162.5 mA h g(-1) is stably maintained at 0.2C during the first 100 cycles.