The photoionization of phenylnitrene was investigated by photoion mass-selected threshold photoelectron spectroscopy in the gas phase. Flash vacuum pyrolysis of phenyl azide at 480 °C produces the nitrene, which subsequently rearranges at higher temperatures affording three isomeric cyanocyclopentadienes, in contrast to low-temperature trapping experiments. Temperature control of the reactor and threshold photoelectron spectra allows for optimizing the generation of phenylnitrene or its thermal rearrangement products, as well as obtaining vibrational information for the corresponding ions. The adiabatic ionization energies (AIE) of the triplet nitrene (³A₂) to the radical cation in its lowest-energy doublet (²B₂) and quartet (⁴A₁) spin states were determined to 8.29 ± 0.01 and 9.73 ± 0.01 eV, respectively. Vibrational frequencies of ring breathing modes were measured at 500 ± 80 and 484 ± 80 cm^-1 for both the X^~(²B₂) and a^~(⁴A₁) cationic states, respectively. The AIE differ from the values previously reported; hence, we revise the doublet–quartet energy splitting of the phenylnitrene radical cation to 1.44 eV, in excellent agreement with composite methods and coupled cluster calculations, but considerably higher than the literature reference (1.1 eV).