A series of BN-incorporated borafluorenate heterocycles, bis(borafluorene-phosphinimine)s (11–15), have been formed via intramolecular Staudinger-type reactions. The reactions were promoted by light or heat using monodentate phosphine-stabilized 9-azido-9-borafluorenes (R₃P-BF-N₃; 6–10) and involve the release of dinitrogen (N₂), migration of phosphine from boron to nitrogen, and oxidation of the phosphorus center (P^III to P^V). Density functional theory (DFT) calculations provide mechanistic insight into the formation of these compounds. Compounds 11–15 are blue emissive in the solution and solid states with absolute quantum yields (Φ_F) ranging from 12 to 68%.