In this study, electrospun carbon nanofibers hybridized with silicon oxide (SiOx) are prepared by using a syringeless electrospinning system of polyacrylonitrile (PAN) solution containing tetraethylorthosilicate (TEOS) via a sequential pyrolysis process. The syringeless electrospinning system provides a large number of composite nanofibers in a short time, and the obtained composite nanofibers exhibit uniform diameter and morphology. The composite nanofiber is converted into a carbon nanofiber containing SiOx via a simple pyrolysis. The obtained SiOx‐carbon nanofiber mat exhibits higher charge/discharge capacity than a general carbon nanofiber, and it provides more stable retention than single crystalline silicon materials. Thus, the mass‐production of a SiOx‐carbon nanofiber from syringeless electrospinning is a promising method to produce anodic materials for Li‐ion batteries. A silicon oxide (SiOx)‐carbon nanofiber for anode material of a lithium‐ion battery is prepared via a syringeless electrospinning system and simple pyrolysis. The anode material with the SiOx‐carbon nanofiber exhibits higher charging/discharging capacity when compared to that of carbon material and better retention capacity when compared with that of silicon materials.