One-dimensional silicon oxycarbide (SiOC)/C composite nanofibers were fabricated by electrospinning and subsequent heat treatment. Introducing carbon matrix to SiOC anode material is an efficient way to accommodate the large volume changes during cycling and also increase the amount of free carbon, which is beneficial for improving the reversible capacity. These SiOC/C composite nanofibers form free-standing conductive membranes that can be used directly as battery electrodes without adding carbon black or polymer binder. Results show that after 80 cycles, the discharge capacity of SiOC/C composite nanofiber anodes is 70% higher than that of Si/C nanofiber anodes and more than 1.5 times larger than those of commercial anodes made from graphite. It is, therefore, demonstrated that one-dimensional SiOC/C nanofibers are promising anode material with large capacities and good cycling stability.