Electrospinning is a technique that produces sub-micron sized continuous fibers by electric force from polymer solutions or melts. Due to its versatile manufacturability and the cost effectiveness, this method has been recently adopted for the fabrication of one-dimensional materials. Here, we fabricated polyacrylonitrile (PAN) polymer fibers, from which uniform carbon fibers with diameters of 100-200 nm were obtained after carbonization at 800 oC in N2. Special emphasis was directed to the influence of the phase separated polymer solution on the morphology and the microstructure of the resulting carbon fiber. The addition of poly(styleneco-acrylonitile) (SAN) makes the polymer solution phase separated, which allows for the formation of internal pores by its selective elimination after electrospinning. XPS and Raman Spectroscopy were used to confirm the surface composition and the degree of carbonization. At the PAN:SAN = 50:50 in vol%, the uniform carbon fibers with diameters of 300~500 nm and surface area of 131.6 m2g-1 were obtained.