In this study, carbon nanofibers (CNFs) were grown by chemical vapor deposition on C-fiber textiles that had Ni and Cu catalyst deposited via electrophoretic deposition. Before the CNFs were coated with silica layer via hydrolysis of TEOS (Tetraethyl orthosilicate), the carbon nanofibers were oxidized by nitric acid. Due to oxidation, the hydroxyl group was created on the carbon nanofibers and this was used as an activation site for the SiO2. The physicochemical properties of the grown carbon nanofibers were investigated with Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS), X-ray Diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The structures of SiO2-coated carbon nanofibers were characterized by XPS and TEM. The electrochemical properties and the capacitance of the materials were investigated by galvanostatic charge-discharge and cyclic voltammetry. Different types of carbon nanofibers were grown upon the deposition utilizing catalysts, with the SiO2 uniformly coated on the surface of carbon nanofibers. When used as an anode material for the Li secondary battery, the SiO2/CNFs composite had a lower capacity maintenance and a greater discharge capacity as compared to the carbon nanofibers.