Fluorescence and fluorescence excitation spectra of the photolysis products of perfluorophenyl azide and perfluoro-2-naphthyl azide in n-hexane and n-heptane at 5 K were recorded. The spectra with (0,0) transitions at 18 800 and 18 300 cm(-1) were assigned to perfluorophenyl nitrene and perfluoro-2-naphthyl nitrene, respectively. A narrow spectrum with a (0,0) transition at 17 300 cm(-1) was attributed to the aryl aminyl radical derived from perfluoro-2-naphthyl nitrene formed by abstraction of a hydrogen atom from the surrounding solvent matrix. The experimental results are consistent with calculations using semiempirical, B3LYP, and CASSCF/CASPT2 methods.