PURPOSE: To enable the production of 1,3-dioxolane of high purity by allowing the vapor containing 1,3-dioxolane and water to come into contact with a liquid containing ethylene glycol in the distillation column.

CONSTITUTION: 1,3-Dioxolane containing water of low concentration is fed into a 1,3-dioxolane distillation column, while a liquid preferably containing more than 20% of ethylene glycol is introduced from the column top into the column so that their vapor-liquid contact is effected whereby the objective purification is attained.