Porous carbon spheres with hierarchical pore structure were prepared by an aerosol method from glucose, the formation process was proposed, and the electrochemical performance of the sample was evaluated in both KOH and TEA-BF4/AN electrolyte. Due to the hierarchical pore structure, high specific surface area and spherical morphology, the sample demonstrated excellent electrochemical performance. The specific capacitance of the material in KOH and TEA-BF4/AN was up to 240 and 80 F g(-1), respectively, and the capacity retention was about 77% when the current density increased to 10 A g(-1) in KOH. It was worth noting that the specific capacitance decreased little even when the mass loading increased to 10.5 mg and the current density increased to 5 A g(-1), which was potential for the large-scale utilization of the material as electrode.