Porous carbon with various structures from micropores (< 2 nm) to hierarchical pores (0-4 nm) was synthesized from biomass waste mangosteen peels via KOH activation process. Microporous carbon was obtained mainly at a low activation temperature of 700 A degrees C or a low alkali/carbon of 3. Hierarchical porous carbon with ultrahigh surface area (> 3000 m(2) g(-1)) and pore volume (> 1.4 cm(3) g(-1)) was obtained at alkali/carbon ratio higher than 3.5 and activation temperature of 800 A degrees C. Sulfur with a high content of 65 wt% was able to be fully accommodated into the pores of hierarchical porous carbon to form C/S composite cathode for lithium sulfur battery while in the case of microporous carbon, residual sulfur on carbon surface was detected. High specific discharge capacities of more than 800 mAh g(-1) were achieved from hierarchical porous carbon/S composites at 0.5 C, and the sample synthesized at alkali/carbon of 4 and activation of 800 A degrees C exhibits the best cycling performance. After 500 cycles at 0.5 C, a high discharge capacity of 509 mAh g(-1) was maintained, indicating an excellent capacity retention. Relationship between pore characteristics of porous carbon and the electrochemical performance of its sulfur composite was discussed.