In this work, we fabricated superhydrophobic electrochemical carbon fibers (CFs) with double-scale roughness by the growth of graphite nanofibers (GNFs) on CF surfaces. High-density GNFs were synthesized by the chemical decomposition of C2H2 on CF surfaces coated with a Ni-doped mesoporous TiO2 film at lower temperature. SEM and TEM results indicated that GNFs with an average diameter of 40 nm grew uniformly and densely on CF surfaces. The contact angle of the CF surfaces increased from 27.2 degrees to 153.5 degrees after growth of GNFs and coating of fluoropolymer. And, the electrochemical performances of GNFs decorated CFs electrodes were used in electrochemical capacitors. The electrochemical properties were carried out using cyclic voltammetry method and galvanostatical charge/discharge techniques. The results showed that the growth of GNFs on CF surfaces provided the highest specific capacitance. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.