In this work, LiMn₂O₄ powder synthesized by sol-gel method using tartaric acid as chelating agent was mixed with polyethylene oxide (PEO) to form a solution of LiMn₂O₄/PEO. The polyethylene oxide/lithium manganese oxides (LiMn₂O₄/PEO) solution in ethanol was electrospun to produce cathode nanofiber materials. The effect of different concentrations of LiMn₂O₄ (5%, 7% and 9%) on fiber formation was also studied. After calcination, nanoparticles of LiMn₂O₄ with less than 100 nm were successfully obtained. The structure and properties of fabricated electrospun LiMn₂O₄ nanofiber and nanoparticles were studied using field emission scanning electron microscopy (FESEM), X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). Electrospinning succeeded in forming clear interwoven spider web nanofiber with no bead formation. The results showed that the particle size increased with increasing LiMn₂O₄ content. Conductivity studies show that the very small particle size resulted in low conductivity performance. The cell with configuration Li/1M LiPF₆ in EC/DMC/ LiMn₂O₄ has given an open circuit voltage (OCV) of ~ 3.0 V.