The Staudinger reduction of heteroaryl azides containing an N-oxide moiety with triphenylphosphine in mixed aqueous/THF solutions yields a mixture of amine and iminophosphorane products. A product analysis study using a combination of 1 H and 31 P NMR spectroscopic techniques indicates that in these systems, even under mild conditions, the amine product is generated, not from the hydrolysis of the iminophosphorane as expected from the standard reaction mechanism, but via hydrolysis of the phosphazide intermediate. The amount of amine generated is dependent on the structure of the starting azides, the composition of solvent, and the reaction conditions. The possible mechanisms of amine formation under acidic, neutral, and basic conditions are discussed.