Sulfur-mediated　synthesis　has　been　demonstrated　as　a　simple　but　efficient　pathway　to　control　the　texture　and　electronic　structure　of　poly(tris-triazine)　based　graphitic　carbon　nitride　semiconductors　with　improved　photocatalytic　reactivity　over　the　pristine　counterpart.　Here,　we　advance　this　strategy　by　employing　cheap　and　easily　available　elemental　sulfur　as　the　external　sulfur　species　instead　of　sulfur-containing　precursors　for　the　sulfur-mediated　synthesis　of　polymeric　carbon　nitride　photocatalysts.　Characterization　results　revealed　that　the　multiple　thermal　condensations　of　carbon　nitride　precursors　in　the　hot　sulfur　flux　provided　a　facile　means　to　promote　the　formation　of　graphitic-like　carbon　nitride　conjugated　systems,　altering　the　traditional　route　of　thermal-induced　self-polymerization　of　melamine.　The　textural,　electronic,　and　optical　properties　of　the　resultants　organic　semiconductors　was　therefore　strongly　modified　to　endow　the　materials　with　improved　physical　and　chemical　properties,　as　demonstrated　by　the　enhanced　photocatalytic　activity　for　water　reduction　and　oxidation　under　visible　light　irradiation　with　wavelength　＞420　nm.　This　result　again　underlines　the　benefit　of　a　sulfur-mediated　approach　to　construct　and　manipulate　polymeric　carbon　nitride　networks　for　sustainable　applications　in　catalysis　and　photocatalysis.　©　2012　American　Chemical　Society.