A novel tremella-like graphene/polyaniline composite was achieved from self-assembly of graphene nanosheets during polymerization of aniline in H2O/N,N-dimethylformamide solution, and was further employed as an electrode for supercapacitors. This graphene/polyaniline composite demonstrates a spherical tremella-like structure and a large specific capacity of 497 F g (1) at a current density of 0.5 A g (1). Particularly, an outstanding rate capability of 456 F g (1) under 5 Ag (1) after 1000 cycles was obtained. Scanning electron microscopy showed that polyaniline nanoparticles were uniformly deposited on free-standing graphene nanosheets, and self-assembled to a spherical tremella-like structure. Therefore, this unique nanostructure is promising for high-performance electrochemical applications. (C) 2014 Elsevier Ltd. All rights reserved.