Mono-, di-, and trifunctional kinetically stabilized aliphatic nitrile N-oxides were synthesized via a two-step process comprising an initial nucleophilic addition of a heteroatomtethering and a carbon-centered nucleophile to a nitroethene and subsequent dehydration of the resultant nitroalkane. We further present the first X-ray crystal structure investigation of an aliphatic nitrile N-oxide. The kinetics of the products' click reactions and DFT calculations confirmed that the obtained nitrile N-oxides had high reactivities.