The electrospinnability of pitch was improved by blending in a solution of polyacrylonitrile (PAN) resulting in the reduction of the average fiber diameter from 2000 to 750 nm. Activated carbon fibers (ACFs) derived by stabilization, carbonization and steam activation at 700, 800, and 900 ${^{circ}C}$ of the PAN/pitch electrospun fibers for 60 min were investigated as electrodes for supercapacitors. The Brunauer, Emmett, Teller (BET) specific surface area ranged from 732 to 1877 $m^2g^{-1}$ and the specific capacitance from 75.5 to 143.5 $Fg^{-1}$, depending on the activation conditions. Electrodes from the electrospun web activated at 900 ${^{circ}C}$ exhibited a particularly quick response showing a high frequency of 5.5 Hz at a phase angle of ?$45^o$ of the impedance spectroscopy.