Fabrication of precursor-derived ceramic fibers as electrode for energy storage applications remains largely unexplored. Within this work, three little known polymer-derived ceramics (PDC)-based fibers are being studied systemically as potential high-capacity electrode materials for electrochemical energy devices. We report fabrication of precursor-derived SiOC fibermats via one-step spinning from varying composition of siloxane oligomers followed by stabilization and pyrolysis at 800 °C. Electron microscopy, Raman, FTIR, XPS, and NMR spectroscopies reveal transformation from polymer to ceramic stages of the various SiOC ceramic fibers. The ceramic samples are few microns in diameter with free carbon phase embedded in the amorphous Si-O-C structure. Free carbon phase improves the electronic conductivity and provides major sites for ion storage, whereas Si-O-C structure contribute to high efficiency. The self-standing electrodes in lithium-ion battery half-cells delivers a charge capacity of 866 mAh g^-1electrode with a high initial coulombic efficiency of 72%.