Various nanostructures of polyaniline (PANI) are fabricated on the surface of carbon cloth (CC) by chemical oxidative polymerization. The surface morphologies and electrochemical properties of the PANI/CC hybrid materials are characterized by scanning electron microscope (SEM), water contact angle (CA), cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) techniques. The morphologies and microstructures of PANI/CC hybrid materials can be controlled by the type of the oxidizing agent. The different morphology of uniformly coated, layer and layer fibrous, ordered needle like PANI built on CC sheet are obtained by using FeCl3, H2O2, MnO2 as the oxidizing agent. The produced hybrid electrode materials are labeled as PANI/CC/FeCl3, PANI/CC/H2O2, PANI/CC/MnO2, respectively. We demonstrated that the morphology of the PANI plays an important role in their electrochemical properties. The porous and ordered needle like PANI/CC/MnO2 exhibits higher specific capacitance (560.5Fg−1 at 1Ag−1) and higher energy density (49.78Whkg−1 at a power density of 400Wkg−1) than PANI/CC/H2O2 and PANI/CC/FeCl3. In addition to this, it also exhibits good long term cycling stability. This work is fully proved that micro-structure can determine the macro-properties by the facts.