The kinetics of methanolysis of substituted benzamide O-(phenoxycarbonyl)- and O-(alkoxycarbonyl)oximes catalyzed by sodium methanolate was studied at 25 °C. The reaction proceeds in two steps. In the first, faster step, the substituted phenoxy group is exchanged for a methoxy group giving rise to substituted O-(methoxycarbonyl)oximes. In the second step, a benzamide oxime is eliminated and dimethyl carbonate is formed. The slope of the plot of the rate constant in dependence on the sodium methanolate concentration has an increasing tendency in both steps. In the presence of 18-crown-6, the plots are linear and the rate constants are lower than in the absence of the crown ether. The rate constants of the reaction of the substrate with the methanolate ion and with the MeONa ion pair were determined assuming that the sodium cation-catalyzed reactions constitute the rate-determining step of the reaction of the substrate with the MeONa ion pair. For the elimination of the aryloxy group and of the substituted benzamide oxime, the rate constants of the reaction with the ion pair are roughly twelvefold and twentyfold higher, respectively, than in the uncatalyzed reaction. The slope of the dependence of log k on the pKa of the substituted phenols (βlg) has the value of -0.52 for the uncatalyzed reaction of elimination of the substituted phenoxy group, -0.83 for the elimination of the benzamide oxime group, and -0.53 for the reaction with the ion pair. In the first step and probably also in the second step, the reaction proceeds by the concerted mechanism. The relatively high ρ value of methanolysis of substituted benzamide O-(4-nitrophenoxycarbonyl)oximes, 0.63, suggests that the structure of the transition state approaches that of the tetrahedral intermediate.