Bi4Ti3O12 nanofibers with diameters of 50-100 nm have been fabricated for the first time through a simple and economical technique of electrospinning combined with subsequent calcination. The as-formed Bi4Ti3O12 nanofibers are porous and composed of inter-linked nanoparticles of 30-50 nm in size. They exhibit both enhanced visible-light-driven photocatalytic decomposition of rhodamine B (RhB) and favorable recycling capability. It is attributed to not only the macrostructure, such as the morphology, surface texture, and grain shape, but also the intrinsic structures of oxygen vacancies and surface adsorbed oxygen.