An efficient method to synthesize benzothieno[3,2-b]benzofurans via intramolecular dehydrogenative C–H/O–H coupling has been developed. Good to excellent yields (64–91%) could be obtained no matter if the substituted group is electron-donating or electron-withdrawing. Notably, three-to-six fused ring thienofuran compounds could be constructed using this method. A reaction mechanism study showed that 1,1-diphenylethylene can completely inhibit the reaction. Therefore, it is a radical pathway initiated by single electron transfer between the hydroxyl of the substrate and the copper catalyst.