Both pure polyimide (PI) and Fe-FeO nanoparticles reinforced PI nanocomposite fibers with a particle loading of 5, 10, 20, and 30 wt % are produced by electrospinning with optimized operational parameters such as polymer concentration, applied electrical voltage, and tip-to-collector distance. The morphology of the resulting products is correlated to the corresponding rheological behaviors of the pure PI and Fe-FeO/PI nanocomposite solutions. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) reveal an enhanced thermal stability of the nanocomposite fibers after introducing the Fe-FeO nanoparticles. The glass transition temperature (T(g)) and melting temperature (T(m)) of the nanocomposite fibers increase by 10-12 and 15-17 degrees C, respectively, as compared to those of the pure PI fibers. The magnetic properties of the Fe-FeO nanoparticles in the polymer nanocomposite fibers are different from those of the as-received nanoparticles. An increased shell thickness by 7.4% is deduced after the nanoparticles experiencing the high-voltage electrospinning.