We demonstrate a simple electrospinning for preparing Si-carbon composite Nanofiber (NF) in which aciniform aggregates of Si particles are well encased by amorphous carbon. The Si-carbon composite NF exhibit a significantly improved electrochemical performance with a high specific capacity of 1250 mAh·g−1 and a superior cycling performance during 50 cycles at a rate of 0.2C. More importantly, Si-carbon composite NF maintain about 70% of initial capacity at 0.2C and an excellent cycling stability even at 25 times higher current density compared to the initial condition, proving that it has superb kinetics compared to ever reported Si or SiOx materials. The electrochemical superiority of Si-carbon composite NF can be attributed to amorphous carbon framework accommodating the inherent volume expansion of Si during lithiation as well as the enlarged contact area between active materials and conducting agent attributed to the morphological characteristics of its one dimensional (1D) nanostructure.