Polyaniline (PANI)/carbon aerogel (CA) composite electrode materials were prepared by chemical oxidation polymerization. The morphology of PANI/CA composite was examined by scanning electron microscopy. The results showed that PANI was uniformly deposited onto the surface of porous CA and filled big inner pores of the CA. Electrochemical performance of the composite electrode was studied by cyclic voltammograms and galvanostatic charge/discharge measurements. The results indicated that the PANI/CA composite electrode had much better electrochemical performance, high reversibility, and high charge/discharge properties than CA. Moreover, the results based on cyclic voltammograms showed that the composite material has a high specific capacitance of 710.7 F g−1, while the capacitance of CA electrode was only 143.8 F g−1. Besides, the supercapacitor using the PANI/CA composite as electrode active material showed a stable cycle life in the potential range of −0.2–0.8 V.