Three copolymers that incorporate dithieno[3,2-b:2',3'-d]pyrrole with fluorene, carbazole, or pyridine have been prepared by Suzuki reaction and characterized by NMR spectroscopy and GPC. A new homopolymer of dithieno[3,2-b:2',3'-d]pyrrole was also synthesized for the comparison of their structure-property relationships. Their thermal, optical, and electrochemical properties have been investigated. All the polymers exhibit good thermal stability with decomposition temperatures around 400 degrees C. The fluorescence quantum efficiencies of all these polymers in solution are in the range of 33.5-55.5%. The copolymers also show high film fluorescence quantum efficiencies of about 20% while the fluorescence of the homopolymer film is almost quenched.