An evolutionary composite of LiFePO4 with nitrogen and boron co-doped carbon layers has been prepared through processing hydrothermal-synthesized LiFePO4 and then successfully applied in LiFePO4 for commercial use, achieving excellent electrochemical performance. It is found that the electrochemical performance can be improved through single nitrogen doping (LiFePO4/C-N) or boron doping (LiFePO4/C-B). When modifying LiFePO4/C-B with nitrogen (LiFePO4/C-B+N), there exists a mass of non-conducting N-B configurations (190.1 eV and 397.9 eV) and it decreases the electronic conductivity from 2.56×10(-2) to 1.30×10(-2) S cm(-1), resulting in weak electrochemical performance. Nevertheless, using the opposite order to decorate LiFePO4/C-N with boron (LiFePO4/C-N+B) can not only eliminate the nonconducting N-B type impurity, but promote a higher level of conductive C-N (398.3 eV, 400.3 eV and 401.1 eV) and C-B (189.5 eV) configurations, which improves the electronic conductivity to 1.36×10(-1) S cm(-1) and leads to synergistic electrochemical activity distinctly compared with single N (or B) doped materials (even much better than the sum of them in capacity at 20C). Moreover, attributed to the electron-type and the hole-type carrier donated by nitrogen and boron atoms, N+B co-doped carbon coating tremendously enhances the electrochemical property: at rate of 20C, the co-doped sample can elevate the discharge capacity of LFP/C from 101.1 mAh g(-1) to 121.6 mAh g(-1), and the co-doped product based on commercial LiFePO4/C shows the discharge capacity of 78.4 mAh g(-1) rather than 48.1 mAh g(-1). Nevertheless, the B+N co-doped sample decreases the discharge capacity of LFP/C from 101.1 mAh g(-1) to 95.4 mAh g(-1), while the commercial LFP/C from 48.1 mAh g(-1) to 40.6 mAh g(-1).