A commercial carbon cloth (CC) sheet is decorated with polyaniline (PANI) nanofibers using in situ polymerization to achieve excellent electrochemical properties for applications as supercapacitor electrodes, which are characterized by electron microscopy, X-ray diffraction, cyclic voltammetry and galvanostatic charge-discharge techniques. The CC serves as an excellent 3D conductive skeleton supporting a highly electrolytic accessible surface area for redox-active PANI and provides a direct path for electrons. The porous and ordered nanostructure of the electrode provides a larger contact surface area for protons getting in and out of active materials and shortens the path length for electrolyte ion transport. Different reacting temperature can result in different structure of polyaniline. With the same weight loading PANI, fibrous PANI deposited on CC sheets from ice water bath exhibited higher specific capacitance (439Fg−1 at 1Ag−1) and energy density (60.83Whkg−1 at a power density of 500Wkg−1) than pure PANI fibers and those deposited on CC sheets under room temperature. The fibrous PANI deposited on CC sheets from ice water bath also exhibits significant rate capability and good long-term cycling stability.