Carbon materials having fibrous structures and large specific surface area have shown the great utility value as an electrode material and catalyst support because they present excellent chemical stability, good ionic fluidity and electrical conductivity. Recently, the combination of carbon nanofibers (CNFs) and transition metal oxides such as NiO are received a great deal of interest as effective electrode materials for high performance electrochemical. In the present work, NiO decorated CNFs materials were prepared by the hydrothermal growth of NiO on the surface of electrospun CNFs at low temperature. For CNFs preparation, the electrospinning method was adopted by using 10% PAN solution with the electrospinning conditions like stock feeding rate of 0.5 ml/h and supplying a constant voltage of 15 kV. The obtained PAN mat was first under gone by stabilization at 280^oC for 2h and then performed the carbonization in a tube furnace under N₂ atmosphere at 800°C for 2 h. The prepared electrospun CNFs and decorated NiO/CNFs were extensively analyzed by various experimental tools such as FE-SEM, TEM, XRD, FTIR and Raman analysis. The structural and crystalline observations deduced the significant and uniform decoration of NiO nanostructures on electrospun CNFs. The decorated NiO/CNFs were applied as electrode for fabricating the electrochemical supercapacitor by measuring cyclicvoltametry (CV) and galvanostatic charge/discharge (GCD). The decorated NiO/CNFs electrode attained the good specific capacitance with excellent rate capability in 1M Na₂SO₄ solution as electrolyte. Therefore, the decorated NiO/CNFs would be highly promising material for high performance supercapacitors.