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 497Fg−1 at a current density of 0.5Ag−1. Particularly, an outstanding rate capability of 456Fg−1 under 5Ag−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.