Kinetic studies on the ammonolysis and aminolysis of phenethyl nitrite were carried out in 61% dioxan–water. Good second-order rate constants were obtained for the reactions except that with trimethylamine which is autocatalysed by the trimethylammonium ion formed. The rate of the trimethylammonium ion catalysed reaction was obtained from the slope of the plots of apparent second-order rate constants against concentration of trimethylammonium ion. There was no general base catalysis in any of the reactions. Solvent kinetic deuterium isotope effects were found to be 1.96 and 2.21 for the reactions with methylamine and morpholine, respectively, and 2.44 for the trimethylammonium ion catalysed reaction with trimethylamine. Brönsted plots are scattered, since substitution of hydrogen by a methyl group on NH₃ markedly increases the nucleophilicity, e.g. the relative rates NH₃ : MeNH₂ : Me₂NH : Me₃N were 1 : 5.5 × 10² : 5.1 × 10⁵ : 5.3 × 10⁶. However, logarithms of the rate constants are correlated linearly with the vertical ionization potentials of these amines. All these results suggest that the reaction is ‘orbital controlled’ and proceeds via concerted displacement of alkoxide by amine rather than addition–elimination. The results are rationalized in terms of the high electronegativity of nitrogen and the presence of a lone pair of electrons on nitrogen.