Spinel LiNi0.5Mn1.5O4 hierarchical nanofibers with diameters of 200-500nm and lengths of up to several tens of micrometers were synthesized using low-cost starting materials by electrospinning combined with annealing. Well-separated nanofiber precursors impede the growth and agglomeration of LiNi0.5Mn1.5O4 particles. The hierarchical nanofibers were constructed from attached LiNi0.5Mn1.5O4 nanooctahedrons with sizes ranging from 200 to 400nm. It is proven that these LiNi0.5Mn1.5O4 hierarchical nanofibers exhibit a favorable electrochemical performance. At a 0.5C (coulombic) rate, it shows an initial discharge capacity of 133mAhg(-1) with a capacity retention over 94% after 30cycles. Even at 2, 5, 10, and 15C rates, it can still deliver a discharge capacity of 115, 100, 90, and 80mAhg(-1), respectively. Compared with self-aggregated nanooctahedrons synthesized using common sol-gel methods, the LiNi0.5Mn1.5O4 hierarchical nanofibers exhibit a much higher capacity. This is owing to the fact that the self-aggregation of the unique nanooctahedron-in-nanofiber structure has been greatly reduced because of the attachment of nanopolyhedrons in the long nanofibers. This unique microstructured cathode results in the large effective contact areas of the active materials, conductive additives and fully realize the advantage of nanomaterial-based cathodes.