Hollow structured graphene-polyaniline spheres (GSA/PANI HS) were prepared via a facile and efficient Pickering emulsion polymerization using sulfonated graphene (GSA) as Pickering stabilizer. In our procedure, amphiphilic sulfonated graphene (GSA) was first synthesized and used to stabilize an oil phase containing aniline. Upon aniline polymerization at the oil/water interface, graphene-polyaniline hollow sphere (GSA/PANI HS) with a rough outer surface and a smooth inner surface, was generated. The size as well as the electrochemical properties of GSA/PANI HS could be easily adjusted by varying the amphipathicity and concentration of GSA, and the oil-water volume ratios of the Pickering emulsions. The synthesized GSA/PANI HS exhibited superior performance in supercapacitors compared to the common stacked two-dimensional GSA/PANI composite owing to its unique hollow structure, which provides a larger accessible surface area and reduces the transport length for both charge and ion The specific capacitance of GSA/PANI HS can reach 546 F g−1, more than two folds higher than stacked two-dimensional GSA/PANI composite. In addition, GSA/PANI HS reveals enhanced capacitance retention at higher scan rates (76% from 5 to 500 mV s−1) and current densities (83.5% from 0.5 to 10 A g−1), demonstrating superior electrochemical accessibility of the 3D hollow nanostructure. Furthermore, good cycling stability is also demonstrated, which render them interesting candidates for future electrochemical energy storage systems. This approach represents a simple, convenient and controllable route for the preparation of hollow graphene-polyaniline nanostructures for high performance supercapacitor applications.