Metal oxides are promising candidates as the anodes of next-generation lithium ion batteries. However, the low electronic conductivities hinder their practical applications. Herein, through a facile calcination process using ammonium bicarbonate (NH4HCO3) as the N source, the nitrogen heteroelement was introduced into the ZnO/CoO micro-/nanospheres, which greatly improves the conductivity of the composites. As the lithium-ion battery anode, the N-doped ZnO/CoO micro-/nanosphere demonstrates much enhanced electrochemical performance. It displays a high initial capacity of 911.8 mA h/g at a current density of 0.2 A/g and long-term cycling stability, with a reversible capacity of 977.8 mA h/g remained after 500 cycles at a current density of 1 A/g. Furthermore, the N-doped ZnO/CoO composite presents an outstanding rate performance, with 605 mA h/g remained even at 5 A/g. The excellent electrochemical properties make N-doped ZnO/CoO micro-/nanospheres a promising candidate as high-performance anodes for next-generation rechargeable LIBs.