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In this paper, we report the electrochemical capacitive properties of polystyrene-based hierarchical porous carbon (PS-HPC) for supercapacitors. Compared to many porous carbons such as a commercially available activated carbon and an ordered mesoporous carbon, PS-HPC has a unique three-dimensionally (3D) interconnected micro-, meso- and macroporous network and thus exhibits faster ion transport behavior and a larger utilization of surface area in electric double layer capacitors. The 3D interconnected meso-and macroporous network originates respectively from the compact and loose aggregation of crosslinked polystyrene-based carbon nanoparticles, and is able to facilitate rapid ion transfer/diffusion rates. Furthermore, PS-HPC's micropores exist from the 3D interconnected network inside these crosslinked polystyrene-based carbon nanoparticles, thus giving an exceptional electrochemically accessible surface area for charge accumulation. As a result, the capacitance retention ratio and capacitance per surface area of PS-HPC at a high sweep rate of 200 mV s(-1) are as high as 84% and 28.7 mu F cm(-2), respectively. These encouraging results demonstrate the promising application of PS-HPC for high performance supercapacitors.