Hybrid nanofibers with different concentrations of multi-walled carbon nanotubes ( MWCNTs) in polyacrylonitrile ( PAN) were fabricated using the electrospinning technique and subsequently carbonized. The morphology of the fabricated carbon nanofibers ( CNFs) at different stages of the carbonization process was characterized by transmission electron microscopy and Raman spectroscopy. The polycrystalline nature of the CNFs was shown, with increasing content of ordered crystalline regions having enhanced orientation with increasing content of MWCNTs. The results indicate that embedded MWCNTs in the PAN nanofibers nucleate the growth of carbon crystals during PAN carbonization.