Polyaniline/single-wall carbon nanotube (PANI/SWCNT) composites were prepared by in situ potentiostatic deposition of PANI onto SWCNTs at the potential of 0.75V versus SCE, with the aim to investigate the influence of microstructure on the specific capacitance of PANI/SWCNT composites. It was found that the specific capacitance of the PANI/SWCNT composites is strongly influenced by their microstructure, which is correlated to the wt.% of the PANI deposited onto the SWCNTs. The optimum condition, corresponding to the highest specific capacitance, 463Fg−1 (at 10mAcm−2), was obtained for 73wt.% PANI deposited onto SWCNTs. The specific capacitance of the PANI/SWCNT composite electrode was highly stable, with a capacitive decrease of 5% during the first 500 cycles and just 1% during the next 1000 cycles, indicative of the excellent cyclic stability of the composite for supercapacitor applications.