The photochemistry of para- and ortho-biphenylyl azides and 1-naphthyl azide was studied by ultrafast spectroscopy. In every case, the singlet azide second excited states were observed by transient absorption spectroscopy and were found to have lifetimes of hundreds of femtoseconds. The decay of the S-2 states of the azides was accompanied by the growth of transient absorption of the corresponding singlet nitrenes. The intermediate S-1 state of the azides could not be observed due to its low instantaneous concentration resulting from fast fragmentation and nitrene formation. Quantum chemical calculations predict that the S2 state of the azide is bound and that there is a much lower barrier toward arylnitrene formation from the S1 state of the azide. Vibrational cooling of para-biphenylnitrene (11 ps) was experimentally observed. The lifetime of singlet ortho-biphenylnitrene was 16 ps in acetonitrile and was not affected by perdeuteration of the aryl ring. The lifetime of singlet 1-naphthylnitrene is 12 ps in acetonitrile at ambient temperature.