A process for preparing n-octadienol comprising the steps of:(i) reacting butadiene with water in an aqueous sulfolane solution having a water/sulfolane weight ratio in the range of 20/80 to 70/30 and containing carbonate and/or bicarbonate ions in the presence of (A) palladium or a palladium compound, (B) a monodentate phosphine of the formula: ##STR1## [wherein R.sup.1 is an aliphatic, alicyclic or substituted or unsubstituted aromatic hydrocarbon group having 1 to 8 carbon atoms; R.sup.2 is hydrogen, methyl, nitro, cyano, methoxy or halogen; n is 0 or 1, x is 0, 1 or 2, and y and z are each 0, 1, 2 or 3, with the proviso that y and z are not concurrently equal to 0 and that x+y+z=3; ##STR2## in an amount of at least 6 moles per gram atom of the palladium and (C) a monodentate tertiary amine having a basicity constant (pKa) of 7 or more in an amount of 1 to 50% by volume based on the sulfolane to form n-octadienol;(ii) subjecting at least part of the reaction mixture obtained in step (i) to extraction with a saturated aliphatic hydrocarbon, a monoolefinic hydrocarbon or an alicyclic hydrocarbon; and(iii) recycling at least part of the extraction residue obtained in step (ii) which contains the catalyst components to step (i).