The present invention provides a process for preparing 1,6-hexanediol having a purity of .gtoreq.99.5% by weight by catalytically dimerizing acrylic esters and catalytically hydrogenating the hexenedioic diesters obtained in this way to 1,6-hexanediol by a) dimerizing C.sub.1- to C.sub.8-acrylic esters in the presence of at least one rhodium compound to give mixtures of predominantly 2- and 3-hexenedioic diesters, b) hydrogenating the resulting dimerizing effluent in the presence of chromium-free catalysts comprising predominantly copper as the hydrogenation component and c) purifying the crude 1,6-hexanediol obtained in this way by fractional distillation.