Process for the preparation of 2,3-dihydro-2,2-dimethyl-7-benzofuranol, comprising the reaction between catechol or 4-tert.butyl catechol and isobutyraldehyde in the presence of catalytic amounts of at least one compound selected from the group consisting of the oxides, hydroxides, alcoholates and carboxylates of metals belonging to the Groups IA, IIA, IIB and VIIB of the Periodic System of the Elements and the subsequent reaction of rearrangement of the products which have been obtained, optionally previously removing one or more low-boiling components, in the presence of a compound having acidic properties, of an organic or a mineral nature. The product is useful in the synthesis of pesticides.