Herein we report on the synthesis and properties of 6,6’-dithienylindigo (DTI), as well as its solubilized N,N’-di(tert-butoxy carbonyl) derivative (BOC-DTI). BOC-DTI can be electropolymerized and thermally-interconverted into films of poly(DTI). Thin films of DTI afford quasi-reversible 2-electron reduction and oxidation electrochemistry, and demonstrate ambipolar charge transport in organic field-effect transistors with hole mobility up to 0.11 cm2/Vs and electron mobility up to 0.08 cm2/Vs. Operation of the p-channel shows excellent air stability, with minimal degradation over a 60 day stressing study. Poly(DTI) can be reversibly oxidized and reduced over hundreds of cycles while remaining immobilized on the working electrode surface, and additionally shows a pronounced photoconductivity response in a diode device geometry. This work shows the potential of extended indigo derivatives for organic electronics applications, demonstrating impressive stability in ambient conditions.