The electronic structures of a LiFePO 4 (010) surface adsorbed with C are studied by a first-principles method based on DFT. The results show that the system is more stable when the LiFePO 4 (010) surface is cut through Li atoms. PDOS analysis shows that the electronic structure of atoms in the sub-surface is similar to that of atoms in the bulk. The unpaired electrons in Fe-d orbital play a key role in the changes in the microelectronic structure; these changes lower the band gap and generate new bands that favor the transfer of electrons. Atom C reacts with Fe by chemisorptions when C is adsorbed on the outermost layer. Therefore, the materials may have better electrochemical properties by the improvement of diffusion of both electrons and Li ions when limiting the crystal growth with C coating.