The synthesis and reactivity study of the first isolable boraphosphaketene, cyclic(alkyl)(amino) carbene (CAAC)-borafluorene-P=C=O (2), is described. Photolysis of compound 2 results in the formation of CAAC-stabilized BP-doped phenanthryne (3) through tandem decarbonylation, monoatomic phosphide insertion, and ring-expansion. Notably, while BN-doped phenanthryne was previously discussed as a reactive intermediate which could not be isolated, the heavier BP-doped analogue exhibits remarkable solution and solid-state stability. The reactivity of 2 with stable carbenes was also explored. Addition of CAAC to 2 led to migration of the original CAAC ligand from boron to phosphorus and coordination of the added CAAC to carbon, affording compound 4. Reaction of 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (NHC) with 2 resulted in N-C bond activation to give the unusual spiro-heterocyclic compound (5).