A controlled sol-gel synthesis incorporated with electrospinning is employed to produce polyacrylonitrile-silica (PAN-silica) fibers. Hybrid fibers are obtained with varying amounts of silica precursor (TEOS in DMF catalyzed by HCl) and PAN. Solution viscosity, conductivity, and surface tension are found to relate strongly to the electrospinnability of PAN-silica solutions. TGA and DSC analyses of the hybrids indicate strong intermolecular interactions, possibly between the -OH group of silica and -CN of PAN. Thermal stabilization of the hybrids at 280 °C followed by carbonization at 800 °C transforms fibers to carbon-silica hybrid nanofibers with smooth morphology and diameter ranging from 400 to 700 nm. FTIR analysis of the fibers confirms the presence of silica in the as-spun as well as the carbonized material, where the extent of carbonization is also estimated by confirming the presence of -C═C and -C═O peaks in the carbonized hybrids. The graphitic character of the carbon-silica fibers is confirmed through Raman studies, and the role of silica in the disorder of the carbon structure is discussed.