A novel, highly soluble chromophore for use in organic electronics based on an indigoid structure is reported. Copolymerization with thiophene affords an extremely narrow band gap polymer with a maximum absorption at similar to 800 nm. The novel polymer exhibits high crystallinity and high ambipolar transport in OFET devices of 0.23 cm(2) V-1 s(-1) for holes and 0.48 cm(2) V-1 s(-1) for electrons. OPV device efficiencies up to 2.35% with light absorbance up to 950 nm demonstrate the potential for this novel chromophore in near-IR photovoltaics.