The invention relates to a process for preparing an α,ω-alkanediol comprising the steps of a) reacting an alkanoic acid with an alkanol to give an ester, b) oxidizing at least one terminal carbon atom of the ester by contacting with a whole-cell catalyst, which expresses an alkane hydroxylase, in aqueous solution and in the presence of molecular oxygen, to give an oxidized ester, c) hydrogenating the oxidized ester to form the alkanediol and alkanol, and d) removing the alkanol by distillation, forming a reaction mixture depleted with respect to the alkanol, and recycling the alkanol in step b).