Process for the manufacture of .alpha.-naphthol by hydrolyzing .alpha.-naphthyl esters of aliphatic carboxylic acids in a distillation column by means of steam in counter-current at a particular temperature, and in a certain ratio, in the presence of naphtholsulfonic acids and/or sulfonic acids of naphthyl esters. The .alpha.-naphthol obtainable by the process of the invention is a valuable starting material for the manufacture of dyes, drugs and insecticides, e.g. .alpha.-naphthyl N-methylcarbamate.