A great attention is drawn to lithium-ion batteries (LIBs) by the burgeoning dominance of the technology. Developments in cathode materials that have effectively doubled the capacity within the past few years demand an anode to match. Carbonaceous materials as the most commonly used anode material have been studied and developed immensely in recent years, but they have a serious drawback of low theoretical capacity. This calls for new anode materials to substitute carbon. Si-based anode materials are among the most promising choices for further studies. The reason is that Si is the lightest member of Group IV elements after carbon and shows the highest gravimetric capacities (up to 4000 mAhgr-1 for the end member Li21Si5) although achieving this at ambient temperature is difficult. Thus, even small amounts of Si (20 wt %) in a composite material would lead to impressive results. The formation of lithium intercalation compounds within Silicon is associated with a large volume expansion that results in pulverization of the electrode material and loss of electrical contact between the material grains on prolonged cycling. The resulting rapid capacity fade reduces its practical use as electrode. Many researchers have addressed this problem by using nanometer sized particle to reduce the absolute volume changes of silicon anodes during cycling. Others efforts have been directed toward preparation of composites containing small silicon particles uniformly distributed within an electrochemically active or inactive solid phase and acting as a mechanical and electrochemical buffer. The latter is necessary for preventing electrochemical sintering of the silicon particles which takes place during alloying with Li+. Carbonaceous phases are the logical choice of buffering media for silicon-containing composites, because they are not only electrochemically active, but also have good electrical conductivity and permeability for Li+ .In the present study such a composite has been made by electrodepositing amorphous silicon on carbon nanofiber (CNF) membrane, as an anode material for LIBs. Electrically conductive CNFs are produced by electrospinning and later heat treating polyacrylonitrile (PAN) precursor. Another nanofibrous substrate has been made by electroless plating of Ni on stabilized PAN nanofibers, which is also utilized for silicon electrodepositon to prepare another composite anode material. The electrochemical performances of both of the composite materials have been evaluated in LIB charge/discharge testing. The Si/CNF composite presented a considerable capacity for lithium ions which makes it an ideal candidate for the anode material of high-power LIBs. The other composite having a pre-coat of Ni, which is electrochemically inactive with lithium ions, allowed a more precise evaluation of the Si coat. It is shown that Electrospinning is a straightforward and effective method for producing nanofiber structures that by controlling heat treatment parameters can lead to the production of conductive CNFs which make a promising substrate and a template for the electrodeposition of Si. By controlling the electrodeposition time in – 2.8 V vs. Pt QRE a nanometric layer of Si was formed over the CNFs resulting in randomly distributed Si nanowires. It is envisaged that the resulting composite as the anode material is effective in providing room for expansion and preventing particle re-aggregation in the cycling of LIB. Keywords: Lithium Ion Battery, Anode Material, Silicon, Carbon Nanofiber, Electrodeposition, Electrospinning, Electroless.