Nanofibers with several hundred of nanometers were successfully fabricated using electrospinning process and a mixture of two types of polymers which are: polydimethylsiloxane and polyacrylonitrile as precursors. After stabilization and carbonization at 1000 °C, three phases which are: silicon carbide (SiC), carbon, and oxy‐SiC were presented. Spectroscopic and microscopic techniques had confirmed the presence of nanocrystalline SiC and turbostratic carbons. These phases formed an intertwined network at the nanometric scale. In addition, the resulted fibers showed a core‐skin effect with skin richer in carbon and a core mainly dominated by silicon‐based phases in the form SiC or SiOC ceramics. A significant improvement was observed in both tensile strength and elastic modulus in these hybrid fibers. In term of crystallography, these nanofibers seem to exhibit similar microstructure that was observed in Nicalon fiber. However, it was difficult to determine the ratio of these phases and their influence on the physical properties of these hybrid fibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45967.