Here we report our findings in synthesis and characterization of porous Co3O4 nanofibers coated with a surface-modification layer, reduced graphene oxide. The unique porous Co3O4@rGO architecture enables efficient stress relaxation and fast Li+ ions and electron transport during discharge/charge cycling. When tested in a half cell, the Co3O4@rGO electrodes display high Coulombic efficiency, enhanced cyclic stability, and high rate capability (∼900mAh/g at 1A/g, and ∼600mAh/g at 5A/g). The high capacity is contributed by a stable capacity yielded from reversible conversion reactions above 0.8V vs. Li/Li+, and a increasing capacity induced by the electrolyte decomposition and interfacial storage between 0.8 0.01V during discahrge. A full cell constructed from a Co3O4@rGO anode and a LiMn2O4 cathode delivers good capacity retention with operation voltage of ∼2.0V. These performances are better than those of other full cells using alloy or metal oxide anodes. Our work is a preliminary attempt for practicality of high capacity metal oxide anodes in Li-ion batteries used for the electronic devices.