In this paper, a hollow sphere carbon nanotube (CNT) / polyaniline (PANI) composite was prepared by using the Fe3O4 as a template. At the same time, the pure PANI and CNT/PANI composite were obtained with same method without Fe3O4 template. The composition and the morphology of the obtained samples were characterized by the Fourier transform infrared spectroscopy and scanning electron microscope. And the electrochemical performances of the obtained materials were tested by the cyclic voltammogram, galvanostatic charging/discharging and cycle life testing. The results show that the obtained hollow sphere CNT/PANI composite have larger surface area than pure PANI and CNT/PANI composite for its hollow sphere structure. The obtained hollow sphere CNT/PANI composite have 185 F/g specific capacitance (in organic electrolyte), which is much more than those of the pure PANI and CNT/PANI composite (about 65 F/g, 152 F/g). The results also show that CNT have a great effect on the preparation of the hollow sphere CNT/PANI composite.