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.