In order to explore the e®ect of hierarchical porous carbon on the performances of Li-S batteries, we synthesized three kinds of micro-/meso-/macroporous carbon materials with di®erent pore properties by facile hard-template method. Di®erent from the majority of reports on porous carbon ensuing large speci¯c surface area (SSA) and total pore volume, it was found that in the case of identically high sulfur content, the pore size distribution substantially in°uences the performances of Li-S batteries rather than the SSA and total pore volume. Furthermore, in the assembly of micro-/meso-/macropores, the micropore volume ratio to the total pore volume is dominant to the capabilities of batteries. Among the samples, the porous carbon carbonized with the precursor of sucrose at 950 C presents the highest initial discharge speci¯c capacity of 1327 mAh/g and retention of 630 mAh/g over 100 cycles at 0.2C rate along with the best rate capability. This sample possesses the largest micropore volume ratio of 47.54% but a medium SSA of 1217 m 2 /g and inferior total pore volume of 0.54 cm 3 /g. The abundant micropores e®ectively improve the conductivity of dispersed sulfur particles, inhibit the loss of sulfur series and enable the cathode to exhibit superior electrochemical performances.