One of the few methods for synthesis of 1,6-dioxapyrenes is the acid catalyzed cyclization of 2,6-disubstituted 1,5-bis(2-oxoalkoxy)naphthalenes. The scope and limitations of this reaction has been investigated and 11 new 2,7-disubstituted 1,6-dioxapyrenes have been prepared and characterized. Most of the compounds undergo two reversible oxidations to give the corresponding radical as well as di- cations.