A novel hierarchical porous carbon-carbon nanotube hybrid (HPCC) is prepared using a one-step strategy that uses nickel nanoparticles as the template for pore formation and at the same time, as the catalyst for carbon nanotube (CNT) growth. Such a structure can not only store sulfur in the micro- and mesopores, which restrict the shuttling of polysulfides, but also ensure good electrical conductivity of the whole system due to the incorporation of CNTs. The hierarchical porous structure also ensures fast mass transportation. These factors effectively guarantee the high electrochemical performance of sulfur stored in this carbon in lithium-sulfur batteries.