AbstractAnatase TiO2, as an anode material, has the advantages of good stability, high safety, and low cost; however, the low specific capacity limits its practical application. The strategy of polypyrrole in‐situ coating combined with pyrolysis was adopted in this work to improve its specific capacity. Besides, modified TiO2 composites [((N/S)‐TiO2@C‐shere] co‐doped with nitrogen/sulfur and coated by carbon nanospheres were synthesized. These composites were characterized by SEM, TEM, XRD, FTIR, XPS, BET, and TGA, and their electrochemical performance was studied by the Galvanostatic charge‐discharge test and EIS measurement. The results indicated that when the dosage of pyrrole used was 1 mL, the prepared (N/S)‐TiO2@C‐shere‐1 composite had the maximum discharge specific capacity of 698 mAh g−1 in the 1st cycle and then remained at ∼520 mAh g−1 from the 2nd cycle. It was more than about 3.1 times the actual specific capacity of anatase TiO2 (167.5 mAh g−1) and 1.4 times the theoretical specific capacity of graphite (372 mAh g−1), much higher than that of modified TiO2‐based anode materials reported in references. Moreover, the (N/S)‐TiO2@C‐shere‐1 showed excellent rate capability and ∼100 % coulomb efficiency, exhibiting an excellent application prospect as an anode material of lithium‐ion batteries.