Porous carbon-rich SiOC ceramic aerogels have been synthesized from a linear polysiloxane cross-linked with divinylbenzene (DVB) via hydrosilylation reaction in presence of a Pt catalyst and acetone as a solvent. The obtained wet gels are aged in solvent followed by drying under supercritical conditions using liquid carbon dioxide. The resulting pre-ceramic aerogels are subjected to pyrolysis at 1000°C under controlled argon atmosphere to form the desired SiOC aerogel. The synthesized SiOC ceramics contain 43wt% of free carbon, which is segregated within amorphous SiOC matrix. The high BET surface area up to 230m2g−1 of preceramic aerogels is only slightly diminished to 180m2g−1 after pyrolysis at 1000°C. The electrochemical characterization reveals a high specific capacity of more than 600mAhg−1 at a charging rate of C (360mAg−1) along with a good cycling stability. At a rate of 10C (3600mAg−1) the specific capacities as high as 200mAhg−1 are recovered. The excellent properties of the materials are discussed with respect to their structural features. The porous nature of the carbon rich ceramics allows for fast ionic transport and helps to accommodate the structural changes which in turn allow a stable performance during repeated lithiation/delithiation.