Polystyrene-derived carbon with hierarchical macro-meso-microporous structure was prepared via a simple template-free method. As anode materials for lithium-ion batteries, the as-prepared hierarchical porous carbon (HPC) exhibited good electrochemical performance, attaining a stable capacity of 410 mAh g(-1) for over 100 cycles. It was also highlighted that, HPC showed an excellent high-rate performance in contrast to other amorphous carbon materials. These good lithium storage performances could be attributed to the developed nanostructures of HPC: (1) The continuous macro-/meso-pores were believed to facilitate rapid ion transport by serving as ion-buffering reservoirs/ion-transport pathways, especially at high current densities; (2) The small-sized nanopores including small mesopores and micropores in carbon nanoparticles provided many active sites for Li+ storage reaction; and (3) The as-constructed continuous carbon nanonetwork also represented an excellent conductive skeleton throughout the material. We hope that this class of HPC provides new opportunities for anode materials of LIBs.