WS2-W-WC embedded carbon nanofiber composites were fabricated by using electrospinning method for use in high-performance supercapacitors. In order to obtain optimum electrochemical properties for supercapacitors, WS2 nanoparticles were used as precursors and the amounts of WS2 precursors were controlled to 4 wt% (sample A) and 8 wt% (sample B). The morphological, structural, and chemical properties of all samples were investigated by means of field emission photoelectron spectroscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. These results demonstrated that the embedded phases of samples A and B were changed from WS2 to WS2-W-WC through carbothermal reaction during carbonization process. In particular, sample B presented high specific capacitance (~119.7 F/g at 5 mV/s), good high-rate capacitance (~60.5%), and superb cycleability. The enhanced electrochemical properties of sample B were explained by the synergistic effect of the using 1-D structure supports, increase of specific surface area, and improved conductivity from formation of W and WC phases.