Hierarchically pore-structured carbon (HPC) pillars with a high surface area and large pore volume are obtained by pyrolyzing Al-based porous coordination polymers (Al-PCP) and used as a matrix of the sulfur for lithium-sulfur (Li-S) batteries. The structure and electrochemical performance of the sulfur-impregnated HPC are characterized. The improved performance of the composite is ascribed to the unique porous structure of the HPC matrix and its strong interaction with sulfur. (C) 2013 Elsevier Ltd. All rights reserved.