AbstractGas‐phase elimination reactions of number ofN‐substituted diacetamides have been studied. The rates ofN‐phenyl, 4‐methoxyphenyl, 4‐nitrophenyl, and benzyl diacetamide have been measured between 643–683, 642–693, 673–725, and 555–610 K, respectively. They undergo unimolecular first‐order elimination reactions, for which logA= 12.8, 12.9, 12.8, and 11.0 s−1and Ea= 185.7, 191.4, 193.4, and 143.6 kJ mol−1, respectively. The reactivity of these compounds has been compared with the unsubstituted diacetamide at 600 K. The kinetic data reveals that each of theN‐aryldiacetamides is less reactive than the parent molecule. We attribute this observation to the resonance of the lone pair of electrons on the nitrogen with either the two carbonyl oxygen atoms or with the 6π electrons in the aromatic ring which will result in the stabilization of theN‐aryldiacetamides related to the parent molecules.