Polyaniline is one of the most common electrode materials for supercapacitors. The morphology of polyaniline directly affects the properties of polyaniline. In this paper, a new method for preparing hollow polyaniline nanospheres is described. Polyaniline-S with solid and hollow structures are successfully synthesized by the hydrothermal method, through varying the amounts of the catalyst and oxidant. The prepared hollow nanospheres have uniform particle size, a smooth surface, and uniform wall thickness. The hollow structure provides rapid permeability to the material, facilitating the transfer and transport of charges and ions in the electrolyte, and it can also act as an ion storage tank to increase the accumulation of ions inside. The specific capacitance of polyaniline-S is high at 235 F g-1 at 0.5 A g-1. To reduce the aggregation of polyaniline-S and improve the electrochemical activity, polyaniline-S, and graphene oxide are composited using the interfacial electrostatic interaction. The content of graphene oxide has a significant influence on the electrochemical performance of the composites. The specific capacitance of the polyaniline-S/ graphene oxide composite with a 10% loading amount of graphene oxide reaches 535 F g-1 at 0.5 A g-1, increase of nearly 128% compared to representing a significant polyaniline-S. The specific capacitance retention rate is 93.6% after 10,000 cycles.