Polyacrylonitrile (PAN)/clay – montmorillonite / silica composite nanofibers were prepared via directly electrospinning (ES) process. The X – ray diffraction (XRD) measurements, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) observations of the obtained nanofibers showed that the nano-materials are well dispersed in the polymeric nanofiber having 100-350 nm in diameter. SEM and TEM images show that beads are formed and inorganic filler start to aggregated when the inorganic filler content is higher 3.0 wt.% in nanofibers. The effect of the type and the amount of nanoparticles on the thermal stabilities of the composite nanofibers were studied by termogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques. It was found that incorporation of the proper content of nanoparticles into the PAN fibers results in the composite nanofibers with highly enhanced thermal stabilities compared with the PAN nanofibers