Bulk silicon oxycarbide derived ceramic nanocomposites have been prepared by the application of the conventional ceramic processing to preceramic materials. Tetraethylortosilicate/ polydimethylsiloxane preceramic materials obtained by sol-gel process were thermally treated and attrition milled to 4 micrometers. Subsequently, the preceramic powders were pyrolized at 1100 °C to obtain silicon oxycarbide powders that were pressed and sintered at 1550 °C up to 16 hours. Silicon oxycarbide glasses obtained at 1100 °C from pyrolysis of preceramic materials consist of a Si-O-C network and a carbon like graphite phase well dispersed. At annealing temperatures higher than 1100°C silicon oxycarbide glasses undergo a rearrangement which involves a phase separation to silica and silicon carbide and a segregation of carbon like graphite phase. At these temperatures the material can be considered as a glassy matrix nanocomposite. At temperatures higher than 1500 °C the carbothermal reduction occurs with the consumption of both silica and free carbon phase. However, the nanocomposite structure is maintained but with different constituents. The silicon oxycarbide glasses obtained at 1100 °C are amorphous. However, as a result of all involving processes taken place during the ceramic process, the nanocomposites formed at 1550 °C comprise a silica matrix and nanodomains of carbon like graphite and silicon carbide both of them displaying an incipient crystallization. Structure and crystalline size evolution, from preceramic materials to silicon oxycarbide derived nanocomposites, have been determined by FT-IR and Raman spectroscopies, XRD and 29Si-MASNMR.