Dithieno[3,2-b:2',3'-d]pyrrole-arylene copolymers have been prepared via Stille coupling to produce soluble, processable materials with good molecular weights. Solution and solid-state characterization of the copolymers is described, including photophysical and electrochemical studies, and these properties are compared to those of the parent poly(dithieno[3,2-b:2',3'-d]pyrrole)s as well as analogous bithiophenearylene copolymers. Poly(N-decyldithieno[3,2-b:2',3'-d]pyrrole) and the newly generated copolymers were then used as emissive layers to fabricate initial LEDs, and the initial evaluation of their device performance is presented.