Abstract: Our previous studies have demonstrate the usefulness of dienedione as versatile intermediates for the synthesis of cyclopentenone and arylfuran. The dienedione moiety may serve as a four carbon unit which can undergo consecutive nucleophilic addition reaction to form heterocycles. Herein we report our investigation on the addition of sulfur to the four carbon unit of dienedione for the synthesis of 2,5-disubstituted thiophenes. The regioselectivity of the reaction under various conditions will also be discussed.