In this paper, MnO-carbon hybrid nanofibers are fabricated via an electrospinning method, while polyvinyl alcohol (PVA) and manganese acetylacetonate are used as raw materials. Composition, phase structure, and morphology of the products obtained under different sintering temperatures are studied with modern analytical instruments, and the electrochemical properties of the MnO/C fibers used as the lithium ion battery anode are also studied by continuous charge/discharge procedures. The results demonstrate that sintering temperature has an important influence on the performance of the obtained composites, and there is an optimum value for synthesizing MnO/C composites. Material synthesized under 600 degrees C can exhibit an ideal fiber appearance with MnO particles embedded into the material and deliver the highest capacity among all samples. The formation mechanism of the materials is also analyzed in detail in this paper.