Co3O4 anode materials exhibit poor conductivity and a large volume change, rendering controlling of their nanostructure essential to optimize their lithium storage performance. Carbon-doped Co3O4 hollow nanofibers (C-doped Co3O4 HNFs), for the first time are synthesized using bifunctional polymeric nanofibers as template and carbon source. Compared with undoped Co3O4 HNFs and solid Co3O4 NFs, C-doped Co3O4 HNFs feature a remarkably high specific capacity, excellent cycling stability, and superior rate capacity as anode materials for lithium-ion batteries. The superior performance of C-doped Co3O4 HNFs electrodes can be attributed to their structural features, which confer enhanced electron transportation and Li+ ion diffusion due to C-doping, and tolerance for volume change due to the 1D hollow structure. Density functional theory calculations provide a good explanation of the observed enhanced conductivity in C-doped Co3O4 HNFs.