Polythionphene (PTH)/polyaniline (PANI)/activated carbon (AC) composites as electrode materials for supercapacitors were synthesized by in-situ polymerization of thionphene on PANI/AC. The surface morphology and the molecular structure of the composites were examined by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The electrochemical performances were tested by cyclic voltammetry, Galvanostatic charge-discharge and electrochemical impedance spectrometry. Results show that the PTH/PANI/AC composites exhibit better large current charge-discharge performance and higher capacitance than those of PANI/AC. The capacitance value of the composites would reach 597.4 F/g. The PTH/PANI/AC composites also have better cycle stability than that of PANI/AC.