In a process for separating liquid mixtures comprising formaldehyde, trioxane, alcohol, hemiformal formed from the formaldehyde and the alcohol, usual minor components and up to 5% by weight of water, the liquid mixture is distilled batchwise or continuously at reduced pressure, atmospheric pressure or superatmospheric pressure in suitable apparatuses which are to be connected to one another in an appropriate manner, and the trioxane is produced in very high purity. The other materials of value, formaldehyde and alcohol, present in the mixture can likewise optionally be separated off and recycled or used otherwise, while the minor components are ejected.