In this paper, the CNT was used as the reinforcing material to overcome the PPy swelling and shrinkage during the doping-undoping process. The electrochemical capacitance is about 25 F/g in organic electrolyte. The PPy/CNT composite (2:1, m/m) was prepared by depositing the polypyrrole onto functionalized multi-walled CNT in aqueous-methanol solution via chemical polymerization. The obtained composite material was characterized by scanning electron microscopy and infrared spectrum. And the electrochemical performance of the composite material was tested by cyclic voltammetry and galvanostatic charging–discharging cycling. The results showed that the obtained polymer was the PPy and sheet; moreover, the PPy was coated on surface of the CNT. The electrochemical capacitance was about 154.5 F/g (organic electrolyte), which was about 6 times that of pure PPy (about 25 F/g).