Ordered porous cabon with a 2-D hexagonal structure, high specific surface area and large pore volume was synthesized through a two-step heating method using tri-block copolymer as template and phenolic resin as carbon precursor. The results indicated the electrochemical performance of the sulfur/carbon composites prepared with the ordered porous carbon was significantly affected by the pore structure of the carbon. Both the specific capacity and cycling stability of the sulfur/carbon composites were improved using the bimodal micro/meso-porous carbon frameworks with high surface area. Its initial discharge capacity can be as high as 1200 mAh·g−1 at a current density of 167.5 mA·g−1. The improved capacity retention was obtained during the cell cycling as well.