PURPOSE: To obtain the subject compound useful as a raw material for producing medicines, etc., in high purity and yield by subjecting allyl acetate to alcoholysis with an alcohol having a boiling point higher than that of allyl alcohol in the presence of a catalyst such as an acid.

CONSTITUTION: Allyl acetate is subjected to alcoholysis with an alcohol having a boiling point higher than that of allyl alcohol in the presence of an acid or basic catalyst. The alcoholysis products are distilled and the distillate containing allyl alcohol and allyl acetate is distilled from a distillation tower top, and from the tower bottom, liquid containing the alcohol used for alcoholysis and acetic acid ester of this alcohol is distilled to separate the former two from the latter two. At proper amount of water is added to the former distillate containing allyl acetate and allyl alcohol and the mixture is charged into the next distillation tower and three-component azeotropic composition of allyl acetate/allyl alcohol/water is formed, and allyl acetate is distilled from the tower top and a liquid containing allyl alcohol is obtained from the tower bottom to provide the objective allyl alcohol.