The synthesis of regioisomeric asterisks ( 5 ) and ( 6 ) incorporating a benzene core with six 1‐naphthylthio or six 2‐naphthylthio arms are reported in search for new materials with optoelectronic properties. The consequences on the extension of a π system surrounding a persulfurated benzene core provide a new avenue to study the structural, photophysical, and chemical properties of such family of all‐organic phosphors. It also diverts the persulfuration mechanism after two radical cyclizations for making a [5]dithiohelicene by‐product ( 7 ), and favors dynamic sulfur component exchange reactions surrounding the core. These exchanges convert asterisks ( 5 ) and ( 6 ), non‐phosphorescent at 20°C to the highly phosphorescent ( 4 ) (ϕ ~ 100%, solid state at 20°C). For asterisks ( 5 ) and ( 6 ), the absence of the typical phosphorescence of the per(phenylthio)benzene core in the solid state at 20°C and the …