Polyaniline (PANI) coated Fe3O4 hollow nanospheres (h-Fe3O4@ PANI) have been successfully synthesized and investigated as anode materials for lithium ion batteries (LIBs). The structure and composition analyses have been performed by employing X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results show a good combination between h-Fe3O4 and PANI with a conductive state. When evaluated as anode materials for LIBs, the h-Fe3O4@PANI nanocomposites exhibit excellent LIB performance with enhanced reversible capacity, good cycling performance and rate capability as compared to h-Fe3O4 and solid Fe3O4 (s-Fe3O4) nanospheres. The improved electrochemical performance of the nanocomposite is considered due to the hollow nature of the products and the coated PANI layers.