MnO-carbon hybrid nanofiber composites are fabricated by electrospinning polyimide/manganese acetylacetonate precursor and a subsequent carbonization process. The composition, phase structure and morphology of the composites are characterized by scanning and transmission electron microscopy, X-ray diffraction and thermogravimetric analysis. The results indicate that the composites exhibit good nanofibrous morphology with MnO nanoparticles uniformly encapsulated by carbon nanofibers. The hybrid nanofiber composites are used directly as freestanding anodes for lithium-ion batteries to evaluate their electrochemical properties. It is found that the optimized MnO-carbon nanofiber composite can deliver a high reversible capacity of 663mAhg−1, along with excellent cycling stability and good rate capability. The superior performance enables the composites to be promising candidates as an anode alternative for high-performance lithium-ion batteries.