One-dimension mesoporous cobalt ferrite (CoFe2O4) nanofibers were prepared by a facile single-nozzle electrospinning technique followed by calcination. The lithium storage properties show that the CoFe2O4 nanofibers obtained at 800 °C deliver an initial discharge capacity of 1888 mAh g−1 and a reversible capacity as high as 942 mAh g−1 after 80 cycles, much higher than those of the samples obtained at 600 °C (1193 and 701 mAh g−1, respectively). The CoFe2O4 nanofibers obtained at 800 °C also demonstrate an excellent rate capability. The improved lithium storage properties of CoFe2O4 nanofibers obtained at 800 °C can be attributed to the unique mesoporous and fibrous structures, as well as the high crystallinity, which provide an easy Li+ diffusion path promote electron transfer, meanwhile preventing volume expansion/contraction during discharge/charge processes.