Oxidative polymerization studies of N-functionalized dithieno[3,2-b:2',3'-d]pyrroles (where substituent = hexyl, octyl, decyl, octadecyl, tert-butyl, 2-ethylhexyl, or p-hexylphenyl) via both chemical oxidation and electropolymerization are presented. While electropolymerized samples are insoluble, it is possible to isolate soluble materials via chemical oxidation methods. Solution and solid-state characterization of the resulting polymeric materials is described, including photophysical and electrochemical studies, and these properties are compared to related polythiophene materials. In addition to reduced band gaps (similar to 1.7 eV), these materials exhibit good red emission with solution quantum efficiencies up to 34%.