2,5-Dimethoxy-2,5-dihydrofurans 1 undergo an acid-catalysedrearrangement to 2-furylcarbinol derivatives 2. The reaction shows to be higly regioselective. The diene 3 is found to be the key-intermediate, and its formation can be utilized for the one-pot preparation of 2-methoxyl-1,6-dioxaspiro[4.4]non-3-en 5.