A micron-sized honeycomb-like carbon material (MHC) is prepared in a facile way using nano-CaCO3 as a hard template. A novel electrode for lithium-oxygen batteries is fabricated and displays a superior discharge capacity as high as 5862 mA h g(-1). The higher electrode space utilization is attributed to its hierarchical pore structure, with intrinsic mesopores in the MHC particles for Li2O2 depositions and macropores among them for oxygen transport.