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Summary: Polyaniline (PANI), a low‐cost conducting polymer with an excellent specific capacitance and a high conductivity, is a promising organic material served for supercapacitor. However, it tends to curl and swell after constant charge and discharge, resulting in poor cycle stability. In this work, we employed the interfacial polymerization route to construct an aniline‐grafting graphene oxide/PANI (GO‐ANI/PANI) composite. The as‐prepared GO‐ANI/PANI composite shows a high specific capacitance (160.5 F g‐1) at 0.5 A g‐1 under the wide potential range from 0.0 to 1.0 V. Importantly, at a high current density (10 A g‐1), the capacitance retains 86% after 3000 cycles due to the enhanced interaction between GO and PANI and good conductive network. It has been demonstrated that the GO‐ANI/PANI composite has a higher specific capacitance and better stability compared with GO/PANI obtained by common method. This study implies that the composite electrode could be a competitive candidate for high‐performance supercapacitor. [ABSTRACT FROM AUTHOR]