Aim ng at improving the high rate capability of spinel lithium manganese oxide (LiMn2O4) cathode, ultralong LiMn2O4 nanofibers are prepared by combination of electrospinning and sol-gel techniques. The effect of processing parameters, including the weight ratio of polyvinylpyrrolidone (PVP) to Li and Mn precursor, calcination temperature and time, on the morphology and the resultant cathode performance of spinel LiMn2O4 nanofiber cathodes have been systematically investigated. Thermal behavior of LiMn2O4 precursor nanofibers is performed on a differential scanning calorimetry-differential thermal analysis (DSC-DTA), indicating the spinel LiMn2O4 began forming at 513°C. The cathode materials appear porous “network-like” morphology with nanosize in diameter (∼170nm), microsize in length (∼20μm) and pure spinel structure, confirmed by scanning electron microscopy (SEM) and X-ray diffractometer (XRD). The ultralong LiMn2O4 nanofiber cathode calcined at 700°C for 8h shows highest capacity and best rate capability. Its discharge capacity is 146mAhg−1 at 0.1C; more importantly, the discharge capacities are 112mAhg−1, 103mAhg−1 and 92mAhg−1 at high discharge rates of 10C, 20C and 30C, respectively.