As a new type of electrodes engineering method with three-dimensional (3D) architecture for 3D rechargeable lithium ion batteries, an electrospinning has been successfully employed to prepare 3D net architectures of anatase TiO2 and spinel Li4Ti5O12 nanofibers. Scanning electron microscopy, X-ray diffraction, cyclic voltammetry and the discharge/charge measurements were used to characterize their structures and electrochemical properties. Our results demonstrated that 3D architectures stacked from a cross-bar array of electrospun anatase TiO2 nanofibers could be accomplished but were destroyed after the insertion of Li ion. Significantly, spinel Li4Ti5O12 could be selected as one of promise candidates for the realization of 3D batteries considering its structure stability of 3D spinel Li4Ti5O12 nanofibers associated with well cyclability.