To develop high capacity electrode materials for lithium-ion battery (LIB), dissimilar materials are mixed and, as a result, carbon nanofibers containing silicon (Si) nanoparticles and its components are successfully created by electrospinning method and some heat treatments. Tetraethoxysilane (TEOS) and Si nanoparticles are adopted as additives of carbon nanofibers because of their huge potential for obtaining high capacity. In this research, therefore, we develop TEOS/Si hybrid carbon nanofibers. Consequently, some samples obtain much higher charging/discharging capacity than the theoretical capacity for graphite (372 mAh/g, LiC6) even after second cycle.