Co3O4/Li2TiO3 composite hollow nanofibers with different molar ratios of Co to Ti were fabricated by integrating electrospinning approach with post-annealing treatment. When applied as lithium ion battery anode material for the first time, the Co3O4/Li2TiO3 (Co:Ti = 10:1) electrode exhibits superior electrochemical properties: (i) high initial discharge capacity (1035 mAh g(-1)); (ii) good cycling performance (1728.9 mAh g(-1) after 212 cycles at 100 mA g(-1)); (iii) outstanding rate performance (1039.3 mAh g(-1) at the current densities of 1 A g(-1)). Enhancement of electrochemical performance may be attributed to the improvement of structural stability and conductivity through Li2TiO3 modification as well as the feature of one-dimensional hollow structure. It is demonstrated that the Co3O4/Li2TiO3 composite hollow nanofibers is a promising anode material for lithium ion batteries.