Triplet phenylphosphinidene was prepared by light-induced elimination of ethylene from the corresponding phenylphosphirane and was characterized by IR and UV/vis spectroscopy together with matching of its spectral data with density functional theory computations. The photolysis of phenylphosphirane in P-3-O-2 doped matrices enabled the spectroscopic identification of a hitherto unknown phenyldioxophosphorane, the long elusive phosphorus analogue of nitrobenzene.