n-Octanol is obtained by (i) reacting butadiene with water in a solution containing water, a carbonate and/or bicarbonate salt of a monodentate tertiary amine, and sulpholane in the presence of a palladium compound and a hydrophilic monodentate phosphine, to form 2,7-octadien-1-ol; (ii) extracting 2,7-octadien-1-ol from at least part of the reaction mixture obtained in step (i) with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon, and recycling the extraction residue to the 2,7-octadien-1-ol synthesis step (i); (iii) subjecting the extract layer containing 2,7-octadien-1-ol as obtained in step (ii) to distillation to distill off a large proportion of the extracting solvent therefrom, followed by distillation in the presence of water, whereby the extracting solvent remaining is distilled off in the form of an azeotropic mixture with water, to obtain a distillation residue; (iv) recovering 2,7-octadien-1-ol from the distillation residue obtained in step (iii) by distillation; (v) hydrogenating the 2,7-octadien-1-ol obtained in step (iv) in the presence of a hydrogenation catalyst to obtain n-octanol; and (iv) recovering n-octanol from the hydrogenation reaction mixture by distillation.