Abstract: A distillation process is used to separate methanol from a mixture of methanol with methyl acrylate or methyl methacrylate, as well as from a mixture of methanol and water with methyl acrylate or methyl methacrylate with the use of an azeotropic solvent, which forms an azeotropic mixture with methanol. In distilling such a mixture by the use of a distillation column:(1) part of the condensate of vapors distilled over from the top of the distillation column top is returned to the top of the column;(2) the remaining condensate is separated into two layers;(3) the upper layer essentially composed of an azeotropic solvent from the two separated layers is fed to an intermediate portion of the distillation column;(4) the lower layer essentially composed of methanol from the above two separated layers is withdrawn from the distillation system; and(5) methyl acrylate or methyl methacrylate, or else, methyl acrylate or methyl methacrylate and water, are recovered from the bottom of the column.