The solvent extraction has been successfully applied to the recovery of methyl-substituted 1,3-dioxane from the aqueous reaction media. Aromatic hydrocarbons used as extractants allowed the removal, from the aqueous phase, of up to 75% of dioxane formed in the one stage reactor-extractor. The concept could be included in a downstream separation scheme for the isolation of 1,3-propanediol from a dilute aqueous solution using reversible reaction of the diol with acetalaldehyde.