The synthesis of thieno[3,2-b]tropones and furo-[3,2-b]tropones by dehyrdrobromination of αα-dibromoketones using lithium carbonate in anhydrous N,N-dimethylformamide is investigated. Synthetic routes to furo[3,2-b]tropone and to three substituted thieno[3,2-b]tropones are presented, and attempts to prepare thieno[3,2-b]tropone are reported. The isolation of a photodimer from the photolysis of 2-methylthieno[3,2-b]tropone in methanol is reported, and a possible structure for this compound is proposed.