Porous Fe2O3 nanotubes have been fabricated by annealing the electrospun precursor nanofibers. Moreover, the mechanism for the formation of the controllable Fe2O3 nanostructures is investigated through manipulating the concentration of the electrospun precursor solution and also discussed based on their morphological evolution processes. When evaluated as anode materials for lithium-ion batteries, the porous Fe2O3 nanotubes exhibit good lithium storage performance with high specific capacity of 1407.9mAhg−1 and good cycling stability (stable up to 250 cycles), which is attributed to the unique morphology of the porous, hollow and continuous one dimensional (1D) nanostructures. These results demonstrate that further improvement or optimization of electrochemical performance in metal oxide-based electrode materials could be realized by the design of 1D nanostructures with unique morphologies.