Photolysis of 1- and 5-aryltetrazoles at 5-10 K using a 266 nm laser immediately generates their triplet excited states, which are characterized by their electron spin resonance (ESR) spectra with zero-field splitting parameters D = 0.12-0.13 cm(-1) and E = 0.002-0.008 cm(-1). Further photolysis of all of the aryltetrazoles affords arylnitrenes (D congruent to 1 cm(-1)), and in the case of 5-aryltetrazoles also arylcarbenes (D congruent to 0.5 cm(-1)). The formation of arylnitrenes from 5-aryltetrazoles, where no aryl-N bond is present, is explained by the photochemical rearrangement of initially formed nitrile imines ArCN+N-R to carbodiimides. The monosubstituted carbodiimide PhN=C=NH isomerizes to phenylcyanamide, PhNH-CN, and photolysis of the latter causes rapid elimination of HCN and formation of phenylnitrene. When N-methyl groups are present in the tetrazoles, methylnitrene, CH3-N, is formed too. In the case of 5-phenyltetrazole, additional hydrogen shift and fragmentation afford cyano- and isocyanonitrenes, NCN and CNN.