Abstract The free-standing Si-coated carbon nanofiber (Si/CNF) mat was fabricated for the anode of lithium ion battery through combining electrospun CNF mat with electrodeposited Si layer. Spaghetti or granule-like Si was obtained by varying the deposition conditions. This Si/CNF mat was directly used as an active material and a current collector as well, which involves neither binders nor additional metal substrate. The best performance was achieved in spaghetti-like Si due to its highly porous nature which can accommodate volume expansion and large surface area which benefit the efficient charge transfer both at Si/CNF interface and at the electrode/electrolyte interface. The optimized Si/CNF mat after annealing at 1000 °C delivered a capacity of 870 mA h g−1 at 1st discharge and 730 mA h g−1 at 50th discharge with a capacity retention of 84%, improving the capacity of pure CNF (280 mA h g−1 at the 50th discharge) by almost three times. In addition, corrosion of the current collector no longer exists in our approach. Our X-ray photoemission spectroscopy and electrochemical analysis revealed that the formation of Si–C bond through high temperature annealing can enhance the adhesion between silicon and carbon at the interface which benefits the cyclic performance of anode ultimately.