Li4Ti5O12 spinel crystal-structured nanofibers were synthesized by merging electrospinning and solid-state reaction. The former method was chosen to increase the surface area of the material, thereby increasing the lithium-ion adsorption /desorption rate and performance. The nanofiber-structured Li4Ti5O12 was treated with a dilute hydrochloric acid solution to extract all Li ions from the lattice so that H4Ti5O12 nanofiber ion sieve was obtained for lithium capture. Nanofiber architecture significantly improves lithium ion adsorption/desorption performance of the ion sieve. Also, it should be noted that cyclic performance of nanofiber ionic sieve higher than traditional solid-state synthesized ion sieves. The results show that the nanofiber ion sieve H4Ti5O12 promising material for lithium extraction from the aqueous environments such as brine, waste water and, geothermal waters.