A novel and controllable approach is developed for the synthesis of MnO nanocrystals embedded in carbon nanofibers (MnO/CNFs) through an electrospinning process. The as-formed MnO/CNFs have a porous structure with diameters of 100-200 nm and lengths up to several millimeters. When used as an anode material for lithium-ion batteries, the resulting MnO/CNFs exhibit superior electrochemical performances with high specific capacity, good cyclability, and excellent rate capability. The unique porous carbon nanofibers (PCNFs) can not only improve the contact area between the electrode and the electrolyte, but also alleviate the impact of the large volume effect of MnO during the electrochemical cycling. It is expected that the present synthetic strategy can be extended to synthesize other nanostructured oxides encapsulated in carbon nanofibers for extensive energy transfer and storage applications.