Monoliths of aromatic sulfur mediated mesoporous carbon were fabricated via an aqueous self-assembly strategy and the species of sulfide, sulfoxide, and sulfone on the surface can be tuned rationally. The resultant S-doped mesoporous carbon exhibited superior performance as supercapacitor electrodes. The controllable modulation of sulfur species provided a possibility to clearly understand the role sulfur playing and allowed mechanistic insight into material requirements for high performance capacitors.