In the acid-catalyzed esterification of mercaptoalkyl alcohols by means of carboxylic acids to form mercaptoalkly carboxylates, formation of undesirable, usually sparingly soluble by-products usually occurs. The process of the invention in the absence of acid catalysts avoids the formation of such by-products. Particularly when the esterification of the invention is carried out as reactive distillation using reactive column and residence vessel, good degrees of conversion can also be obtained without acid catalyst and at the same time the formation of the by-products can be largely avoided.