The photolysis of N3- at 2288 Å hardly differs from that at 2537 Å; both probably involve the n,π* state of N3-. On the other hand, new features are shown by the photolysis at 2139 Å, which is within the charge-transfer-to-solvent (CTTS) absorption band. About 10% of the excited ions undergo ionization and ∼30% produce NH2OH, probably by first being internally converted to the n,π* state. Ammonia is produced from the reduction of hydroxylamine by solvated electrons. This is indicated by the effect of electron scavengers The azide radical appears to abstract H atom from alcohols and, more readily, from acetone and NH2OH. A full mechanism is proposed for the photolysis.