A new single-source precursor has been developed from the hydrothermal reaction of graphite oxide (GO), melamine resin (MR) monomers, and CoCl2 to prepare a sandwich-like hybrid of ultrathin nitrogen-doped graphene (NG) sheets and porous Co3O4 nanospheres (Co3O4/NG). This unique structure endows the Co3O4/NG hybrid with large surface area and enhanced electrochemical performances as both anode material for Li-ion batteries and electrocatalyst for oxygen reduction reaction (ORR). As an anode material, it exhibits high reversible capacity, excellent cycling stability and rate performance (1236 and 489 mAh g−1 over 200 cycles at 0.1C and 2C, respectively; 371 mAh g−1 at 5C). As an ORR electrocatalyst, it shows superior catalytic activity and high selectivity for the four-electron reduction pathway compared to the bare Co3O4 and NG alone. Moreover, the Co3O4/NG hybrid is insensitive to methanol, and is much more stable than Pt/C catalyst over long term operation.