The present invention provides a process for preparing 1,6-hexanediol by hydrogenating dialkyl adipates, alkyl 6-hydroxycaproates, 1,4-cyclohexanedione and 4-hydroxycyclohexan-1-one as ester mixtures comprising impurities, by a) freeing resulting the esterification mixture of excess alcohol and low boilers in a first distillation stage (alcohol removal), b) carrying out a separation of the bottom product in a second distillation stage into an ester fraction substantially free of 1,4-cyclohexanediols and a fraction comprising at least the majority of the 1,4-cyclohexanediols, c) catalytically hydrogenating the ester fraction substantially free of 1,4-cyclohexanediols (ester hydrogenation) and d) in a purifying distillation stage, obtaining 1,6-hexanediol from the hydrogenation effluent in a manner known per se, which comprises selectively hydrogenating the ester mixture before stage a) and/or before stage b) (purifying hydrogenation).