A series of new conjugated copolymers incorporating the redox‐active pyrrolo‐TTF unit has been synthesised. The properties of the polymers have been investigated by cyclic voltammetry and electronic absorption spectroscopy, revealing that the pyrrolo‐TTF behaves very differently to its thieno‐TTF variant. In comparison to thieno analogues, the band gaps of the new polymers are wider than expected due to a decrease in the polarizability of the heteratom (nitrogen vs. sulfur) and steric interactions between repeat units. Whilst the pyrrolo‐TTF units are stronger electron donors than thieno‐TTFs in related structures, the two redox active elements of the new polymers (TTF and conjugated chain) function independently under oxidative conditions.
