A new class of hierarchical structure porous carbon black, carbon nanoballs (CNBs), was generated by solution plasma process (SPP) with benzene. The structural characterization revealed that CNBs have excellent meso–macro hierarchical pore structure, with an averaged diameter size of 14.5 nm and a total pore volume of 1.13 cm3 g−1. The CNBs are aggregated forming inter-connected pore channels in different directions on both the meso- and macrometer length scales. The discharge capacity of CNBs reached 3600 mAh g−1, which exceeded the capacity of Ketjen Black EC-600JD (a commercial carbon black with highest cell performance) by 30–40%. The excellent discharge capacity was contributed by the co-existence of high pore volume and meso–macro hierarchical porous structure. This new class carbon material exhibited higher discharge capacity compared to commercial porous carbon materials, and is possible to apply as the next generation of electrode materials in lithium–air (Li–air) battery. The structural and electrochemical properties accompanied with the synthesis mechanism of CNBs were discussed in details.