Phenolic resin-based carbon nanofibers with a diameter of about 110 nm, the highest electrical conductivity of 5.29 S/cm and highest BET specific surface area of 792.7 m2/g were prepared by electrospinning, followed by successive carbonization. The addition of a high-molecular-weight polymer, poly(vinyl butyral) (Mw = 340,000), and electrolytes, pyridine and sodium carbonate, to the phenolic resin/MeOH solution can effectively form a thinner smooth fiber by electrospinning, and then the as-spun fabrics were successfully carbonized at 900 °C for 2h. Thus the prepared carbonized fabrics are very flexible and showed a thinner diameter, a higher conductivity and a higher specific surface area as already described.