A process for the preparation of pyrocatechol and hydroquinone by reaction of phenol with a peroxidic hydroxylating reagent followed by working-up of the resultant reaction mixture is disclosed. The work-up procedure is carried out in a first rectification column operated under specified conditions and having specified separation stages in a rectification section and a stripping section whereby there is distilled overhead components which boil at a temperature lower than phenol. Taken off from the bottom is a mixture comprising phenol and materials of higher boiling point which are fed into a second rectification column which is also operated under very specified conditions whereby pure phenol is recovered overhead leaving a bottoms comprising phenol pyrocatechol and hydroquinone which are then processed to separate phenol from a mixture of pyrocatechol and hydroquinone.