In order to explore the existence of α-effect in gas-phase SN2@N reactions, and to compare its similarity and difference with its counterpart in SN2@C reactions, we have carried out a theoretical study on the reactivity of six α-oxy-Nus (FO−, ClO−, BrO−, HOO−, HSO−, H2NO−) in the SN2 reactions toward NR2Cl (R = H, Me) and RCl (R = Me, i-Pr) using the G2(+)M theory. An enhanced reactivity induced by the α-atom is found in all examined systems. The magnitude of the α-effect in the reactions of NR2Cl (R = H, Me) is generally smaller than that in the corresponding SN2 reaction, but their variation trend with the identity of α-atom is very similar. The origin of the α-effect of the SN2@N reactions is discussed in terms of activation strain analysis and thermodynamic analysis, indicating that the α-effect in the SN2@N reactions largely arises from transition state stabilization, and the “hyper-reactivity” of these α-Nus is also accompanied by an enhanced thermodynamic stability of products from the n(N) → σ*(O−Y) negative hyperconjugation. Meanwhile, it is found that the reactivity of oxy-Nus in the SN2 reactions toward NMe2Cl is lower than toward i-PrCl, which is different from previous experiments, that is, the SN2 reactions of NH2Cl is more facile than MeCl. © 2013 Wiley Periodicals, Inc.