We report a new one-pot synthetic route to tetrahydrofuran derivatives, which were unexpectedly produced under basic conditions by intramolecular etherification of substituted five-membered cyclic carbonates. For alcohols with vicinal hydroxyl groups, and additional OH groups at the β-position, intramolecular etherification leading to 3-hydroxytetrahydrofuran derivatives was observed. These reactions were studied for compounds having from 2 to 6 hydroxyl groups per molecule, and the mechanism was proposed. The developed method provides a new environmentally friendly approach to the synthesis of five-membered cyclic ether derivatives under non-acidic conditions.