Enantioenriched benzopyrano- and naphthopyrano-fused helical phosphafluorenes have been synthesized by the rhodium-catalyzed enantioselective double [2 + 2 + 2] cycloaddn. of dialkynyl phosphorus compds. with phenol- or naphthol-linked tetraynes. Photophys. properties of these phosphafluorenes are also disclosed. [on SciFinder(R)]