Li-air batteries have a promising future for because of their high energy density, which could theoretically be equal to that of gasoline. However, substantial Li–air cell performance limitations exist, which are related to the air cathode. The cell discharge products are deposited on the surfaces of the porous carbon materials in the air electrode, which blocks oxygen from diffusing to the reaction sites. Hence, the real capacity of a Li-air battery is determined by the carbon air electrode, especially by the pore volume available for the deposition of the discharged products. In this study, a simple and fast method is reported for the large-scale synthesis of carbon nanoballs (CNBs) consisting of a highly mesoporous structure for Li-air battery cathodes. The CNBs were synthesized by the solution plasma process from benzene solution, without the need for a graphite electrode for carbon growth. The CNBs so formed were then annealed to improve their electrical conductivity. Structural characterization revealed that the CNBs exhibited both an pore structure and high conductivity.