In this work, the carbon-free Li4Ti5O12 porous nanofibers (Li4Ti5O12-P-NFs) have been successfully fabricated through an electrospinning approach followed by a one-step solid-state reaction. The structural and morphological characterization indicates that the as-prepared Li4Ti5O12-P-NFs has a spinel Li4Ti5O12 phase and many nanosized pores are homogeneously dispersed in the one-dimensional nanofibers. When used as anode material for lithium-ion batteries, the Li4Ti5O12-P-NFs exhibit excellent battery performances in terms of high-rate capability and ultralong-life stability, which can be attributed to the unique carbon-free porous nanostructure composed of well-crystallized Li4Ti5O12 nanocrystals. Thus, we can speculate that this novel concept may also be applicable to prepare other electrode materials for high-performance lithium-ion batteries.