Benzocarbazoles are a class of essential nitrogen-containing heterocycles, which widely exist in numerous natural products and therapeutic agents.[1] The introduction of a phosphoryl group into the heterocyclic scaffold is an efficient strategy for the development of potential bioactive molecules.[2] Recently, an unprecedented photocatalytic route was successfully developed for the synthesis of benzocarbazole by phosphorylation/cyclization reactions using 3-alkynyl-2-arylindole as a class of novel and efficient skeletons (Scheme 1). With this transition-metal-free photocatalytic procedure, various phosphorylated carbazoles were synthesized with diphenylphosphine oxides as phosphoryl radical precursors.