Computational investigations on the add-promoted hydrolysis of 2-aryl-4,4-dimethyloxazolin-5-one (AMO) and its seven para- and meta-substituted derivatives (with electron-donating groups R = OH, OCH(3), CH(3) and electron-withdrawing groups R =. Cl, m-Cl, CF(3), NO(2)) were presented by the density functional theory (B3LYP) method. Two types of reaction mechanism, N-path and O-path, are taken into account, in which the attacks by water molecules at the C2 and CS are accelerated after the protonation on N3 and carbonyl oxygen atoms, respectively. Our computational results clearly manifest that the hydrolysis of AMOs has an obvious substituent effect at the para and meta positions of the benzene ring by correlating the barrier heights with the Hammett constants of substituents. Furthermore, the N-path shows a normal substituent effect, while the favorable O-path shows a reverse substituent effect. The observed reverse substituent effect in experiment actually springs from the reverse substituent effect of the O-path, not the N-path. The substituent effect of the N-path and O-path can be explained by the electrostatic potential at nuclei (EPN) values and Fukui function, respectively. Our theoretical data provided will allow for a better understanding of the add-promoted hydrolysis mechanism and the observed reverse substituent effect of the AMOs, in nice agreement with the available experimental conclusion.